Polycarbonate copolymer and method of producing the same

ABSTRACT

The problem to be solved by the present invention is to provide a polycarbonate copolymer containing a plant-derived raw material, which is excellent in the mechanical strength and heat-resistant and assured of small refractive index, large Abbe number, small birefringence and excellent transparency. The present invention provides a polycarbonate copolymer containing a constitutional unit derived from a dihydroxy compound represented by the following formula (1) and a constitutional unit derived from an alicyclic dihydroxy compound, wherein the Abbe number is 50 or more and the 5% thermal reduction temperature is 340° C. or more; and a method of producing this polycarbonate copolymer by reacting a dihydroxy compound represented by the following formula (1) and an alicyclic hydroxy compound with a carbonic acid diester in the presence of a polymerization catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.12/305,660, filed Apr. 1, 2009 which is the U.S. national stage ofInternational Application No. PCT/JP2007/062037, filed Jun. 14, 2007,the disclosures of which are incorporated herein by reference in theirentireties. This application claims priority to Japanese PatentApplication JP2006-168929, filed Jun. 19, 2006, the disclosures of whichare incorporated herein by reference in their entireties.

TECHNICAL FIELD

The present invention relates to a polycarbonate copolymer containing aconstitutional unit derivable from a carbohydrate such as starch whichis a biomass resource, which is excellent in the heat resistance,moldability and mechanical strength and assured of excellent opticalproperty such as small refractive index and large Abbe number, and amethod of producing the same.

BACKGROUND ART

A polycarbonate is generally produced using a raw material derived froma petroleum resource. However, due to recent fear of exhaustion ofpetroleum resources, it is demanded to provide a polycarbonate using araw material obtained from a biomass resource such as plant. Also,because of concern that global warming resulting from increase oraccumulation of carbon dioxide emissions may bring about climate changeor the like, it is demanded to develop a polycarbonate using aplant-derived monomer as the raw material and being carbon neutral evenafter treating a disposal use.

Conventionally, a technique of obtaining a polycarbonate by usingisosorbide as a plant-derived monomer and effecting transesterificationwith diphenyl carbonate has been proposed (see, for example, PatentDocument 1). However, the polycarbonate obtained is brown and is notsatisfied. As for the copolymer carbonate of isosorbide and otherdihydroxy compounds, a polycarbonate obtained by copolymerizingbisphenol A has been proposed (see, for example, Patent Document 2), andan attempt to improve the rigidity of a homopolycarbonate composed ofisosorbide by copolymerizing isosorbide and an aliphatic diol has beenmade (see, for example, Patent Document 3).

On the other hand, as for the polycarbonate obtained by polymerizing1,4-cyclohexanedimethanol which is an alicyclic dihydroxy compound, alarge number of proposals have been made (see, for example, PatentDocuments 4 and 5), but these polycarbonates are a low-molecular-weightpolycarbonate having a molecular weight of about 4,000 at most andtherefore, many products have a low glass transition temperature.

In this way, a large number of polycarbonates using isosorbide have beenproposed, nevertheless, a polycarbonate obtained by copolymerizingisosorbide and an alicyclic dihydroxy compound is not reported andoptical constants such as refractive index and Abbe number are also notdisclosed.

Patent Document 1: GB 1079686

Patent Document 2: JP-A-56-55425

Patent Document 3: WO2004/111106

Patent Document 4: JP-A-6-145336

Patent Document 5: JP-B-63-12896

DISCLOSURE OF THE INVENTION Problems to be Resolved by the Invention

The polycarbonates described in Patent Documents 1 to 5 are insufficientin terms of heat resistance and transparency as compared withconventional aromatic polycarbonates derived from a petroleum rawmaterial and can be hardly used for an optical material or a moldingmaterial. Accordingly, it is hoped to develop a high-transparencypolycarbonate having a small refractive index and a small Abbe numberwhile maintaining high heat resistance and transparency of an aromaticpolycarbonate.

The purpose of the present invention is to solve the conventionalproblems described above and provide a polycarbonate copolymercontaining a plant-derived constitutional unit, which is excellent inthe mechanical strength and heat-resistant and assured of smallrefractive index, large Abbe number, small birefringence and excellenttransparency.

Means for Solving the Problems

As a result of intensive studies to solve the above-mentioned purpose,the present inventors have found that a polycarbonate copolymer obtainedfrom a dihydroxy compound represented by the following formula (1) andan alicyclic dihydroxy compound is excellent in the mechanical strengthand heat-resistant and assured of small refractive index, large Abbenumber, small birefringence and excellent transparency. The presentinvention has been accomplished based on this discovery.

That is, the essential features of the present invention consist in [1]to [13] below.

[1] A polycarbonate copolymer containing a constitutional unit derivedfrom a dihydroxy compound represented by the following formula (1) and aconstitutional unit derived from an alicyclic dihydroxy compound,wherein the Abbe number is 50 or more and the 5% thermal reductiontemperature is 340° C. or more:

[2] A polycarbonate copolymer containing a constitutional unit derivedfrom a dihydroxy compound represented by the following formula (1) and aconstitutional unit derived from an alicyclic dihydroxy compound,wherein the ratio of the dihydroxy compound represented by the followingformula (1) and the alicyclic dihydroxy compound to all dihydroxycompounds constituting the copolymer is 90 mol % or more:

[3] The polycarbonate copolymer as described in [1], wherein the ratioof the dihydroxy compound represented by formula (1) and the alicyclicdihydroxy compound to all dihydroxy compounds constituting thepolycarbonate copolymer is 90 mol % or more.

[4] The polycarbonate copolymer as described in any one of [1] to [3],wherein the alicyclic dihydroxy compound contains a 5-membered ringstructure or a 6-membered ring structure.

[5] The polycarbonate copolymer as described in [4], wherein the numberof carbon atoms contained in the alicyclic dihydroxy compound is 30 orless.

[6] The polycarbonate copolymer as described in [5], wherein thealicyclic dihydroxy compound is at least one compound selected from thegroup consisting of cyclohexanedimethanol, tricyclodecanedimethanol,adamantanediol and pentacyclopentadecanedimethanol.

[7] The polycarbonate copolymer as described in any one of [1] to [6],wherein the photoelastic coefficient is 20×10⁻¹² Pa⁻¹ or less.

[8] The polycarbonate copolymer as described in any one of [1] to [7],wherein the Izod impact strength is 30 J/m² or more.

[9] The polycarbonate copolymer as described in any one of [1] to [8],wherein the amount of the generated gas except for a phenol componentper unit area at 110° C. is 5 ng/cm² or less.

[10] The polycarbonate copolymer as described in any one of [1] to [9],wherein a constitutional unit derived from at least one member selectedfrom the group consisting of isosorbide, isomannide and isoidide iscontained as the constitutional unit derived from a dihydroxy compoundrepresented by formula (1).

[11] The polycarbonate copolymer as described in any one of [1] to [10],wherein the reduced viscosity for a concentration of 1.00 g/dl at 20°C.±0.1° C. in a solution of phenol and 1,1,2,2-tetrachloroethane at aweight ratio of 1:1 is 0.40 dl/g or more.

[12] A method of producing the polycarbonate copolymer described in anyone of [1] to [11], comprising reacting a dihydroxy compound representedby the following formula (1) and an alicyclic dihydroxy compound with acarbonic acid diester in the presence of a polymerization catalyst:

[13] The method of producing the polycarbonate copolymer as described in[12], wherein an alkali metal compound and/or an alkaline earth metalcompound are used as the polymerization catalyst.

Effect of the Invention

The polycarbonate copolymer of the present invention has high thermalstability, low refractive index, large Abbe number and small opticalanisotropy. Also, the mechanical strength is excellent and the glasstransition temperature can be adjusted between 45° C. and 155° C.according to usage, which enables providing a material to the field offilm or sheet requiring flexibility, to the field of bottle or containerrequiring heat resistance, and to a wide range of fields including lensusage such as camera lens, viewfinder lens and lens for CCD or CMOS, andusage as a film or sheet such as phase difference film, diffusing sheetor polarizing film utilized in liquid crystal or plasma display devices,as an optical disc, as an optical material, as an optical component oras a binder for fixing a dye, a charge transfer agent or the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view showing an NMR chart of the polycarbonate copolymerproduced in Example 1.

FIG. 2 is a view showing an NMR chart of the polycarbonate copolymerproduced in Example 26.

BEST MODE FOR CARRYING OUT THE INVENTION

The embodiment of the present invention is described in detail below,but the construction requirements described below are mere examples(representative examples) of the embodiment of the present invention andas long as the essential features of the invention are observed, thepresent invention is not restricted to the following contents.

The polycarbonate copolymer of the present invention is characterized bycontaining a constitutional unit derived from a dihydroxy compoundrepresented by the following formula (1) and a constitutional unitderived from an alicyclic dihydroxy compound:

In the present invention, the dihydroxy compound represented by formula(1) includes isosorbide, isomannide and isoidide, which are in astereoisomeric relationship with each other. One of these compounds maybe used alone, or two or more thereof may be used in combination.

Among these dihydroxy compounds, in view of facility of availability andproduction, optical characteristics and moldability, most preferredcompound is isosorbide obtained by dehydration-condensing sorbitolproduced from various starches which are abundantly present as aresource and easily available.

Meanwhile, isosorbide is liable to be gradually oxidized by oxygen andfor preventing decomposition due to oxygen during storage or handling atthe production, it is important to avoid mixing of moisture, use adeoxidizer or keep in a nitrogen atmosphere. When isosorbide isoxidized, a decomposition product including formic acid is generated.For example, if a polycarbonate is produced using isosorbide containingsuch a decomposition product, this causes coloration of the obtainedpolycarbonate or serious deterioration in the physical properties. Also,the polymerization reaction is affected and a polymer having a highmolecular weight may not be obtained, which is not preferred.Furthermore, in the case where a stabilizer for preventing generation ofa formic acid is added, depending on the kind of the stabilizer, theobtained polycarbonate may be colored or seriously deteriorated in thephysical properties. As for the stabilizer, a reducing agent or anantacid is used. The reducing agent includes sodium borohydride, lithiumborohydride and the like, and the antacid includes an alkali such assodium hydroxide, but the addition of such an alkali metal salt is notpreferred, because the alkali metal also serves as a polymerizationcatalyst and when added excessively, makes it impossible to control thepolymerization reaction.

If desired, the isosorbide may be distilled for obtaining isosorbidecontaining no oxidation decomposition product. Furthermore, in the casewhere a stabilizer is blended so as to prevent oxidation ordecomposition of isosorbide, the isosorbide may also be distilled, ifdesired. In such a case, the distillation of isosorbide is notparticularly limited and may be simple distillation or continuousdistillation. After the atmosphere is turned into an inert gasatmosphere such as argon or nitrogen, the distillation is performedunder reduced pressure.

In the present invention, high-purity isosorbide having a formic acidcontent of 20 PPM or less, particularly 5 PPM or less, is preferablyused by performing the above-mentioned distillation of isosorbide. Now,a method for measuring the formic acid content in isosorbide isdescribed later in Examples.

On the other hand, the alicyclic dihydroxy compound which can be used inthe present invention is not particularly limited, but usually, acompound containing a 5-membered ring structure or a 6-membered ringstructure is used. The 6-membered ring structure may be fixed in theform of a chair or boat by covalent bonding. By virtue of the alicyclicdihydroxy compound containing a 5-membered ring or a 6-membered ringstructure, the obtained polycarbonate can be increased in the heatresistance. The number of carbon atoms contained in the alicyclicdihydroxy compound is usually 70 or less, preferably 50 or less, morepreferably 30 or less. As this value is larger, higher heat resistanceis obtained, but the synthesis or purification becomes difficult or thecost becomes high. As the number of carbon atoms is smaller, thepurification is facilitated and the availability becomes easy.

The alicyclic dihydroxy compound containing a 5-membered ring structureor a 6-membered ring structure for use in the present inventionspecifically includes alicyclic dihydroxy compounds represented by thefollowing formula (II) or (III):

HOCH₂—R¹—CH₂OH   (II)

HO—R²—OH   (III)

(in formulae (II) and (III), R¹ and R² each represents a cycloalkylgroup having a carbon number of 4 to 20 or a cycloalkoxyl group having acarbon number of 6 to 20).

The cyclohexanedimethanol which is the alicyclic dihydroxy compoundrepresented by formula (II) includes various isomers where in formula(II), R¹ is represented by the following formula (IIa) (wherein R³represents an alkyl group having a carbon number of 1 to 12). Specificexamples thereof include 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

The tricyclodecanedimethanol and pentacyclopentadecanedimethanol whichare the alicyclic dihydroxy compound represented by formula (II) includevarious isomers where in formula (II), R¹ is represented by thefollowing formula (IIb) (wherein n represents 0 or 1).

The decalindimethanol and tricyclotetradecanedimethanol which are thealicyclic dihydroxy compound represented by formula (II) include variousisomers where in formula (II), R¹ is represented by the followingformula (IIc) (wherein m represents 0 or 1). Specific examples thereofinclude 2,6-decalindimethanol, 1,5-decalindimethanol and2,3-decalindimethanol.

The norbornanedimethanol which is the alicyclic dihydroxy compoundrepresented by formula (II) includes various isomers where in formula(II), R¹ is represented by the following formula (IId). Specificexamples thereof include 2,3-norbornanedimethanol and2,5-norbornanedimethanol.

The adamantanedimethanol which is the alicyclic dihydroxy compoundrepresented by formula (II) includes various isomers where in formula(II), R¹ is represented by the following formula (IIe). Specificexamples thereof include 1,3-adamantanedimethanol.

The cyclohexanediol which is the alicyclic dihydroxy compoundrepresented by formula (III) includes various isomers where in formula(III), R² is represented by the following formula (IIIa) (wherein R³represents an alkyl group having a carbon number of 1 to 12). Specificexamples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol and 2-methyl-1,4-cyclohexanediol.

The tricyclodecanediol which is the alicyclic dihydroxy compoundrepresented by formula (III) includes various isomers where in formula(III), R² is represented by the following formula (IIIb) (wherein nrepresents 0 or 1).

The decalindiol and tricyclotetradecanediol which are the alicyclicdihydroxy compound represented by formula (III) include various isomerswhere in formula (III), R² is represented by the following formula(IIIc) (wherein m represents 0 or 1). Specific examples thereof include2,6-decalindiol, 1,5-decalindiol and 2,3-decalindiol.

The norbornanediol which is the alicyclic dihydroxy compound representedby formula (III) includes various isomers where in formula (III), R² isrepresented by the following formula (IIId). Specific examples thereofinclude 2,3-norbornanediol and 2,5-norbornanediol.

The adamantanediol which is the alicyclic dihydroxy compound representedby formula (III) includes various isomers where in formula (III), R² isrepresented by the following formula (IIIe). Specific examples thereofinclude 1,3-adamantanediol.

Among these specific examples of alicyclic hydroxy compounds,cyclohexanedimethanols, tricyclodecanedimethanols, adamantanediols andpentanecyclopentadecanedimethanols are particularly preferred, and inview of facility of availability and handling,1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,2-cyclohexanedimethanol and tricyclodecanedimethanol are preferred.

Incidentally, the compounds illustrated above are mere examples of thealicyclic dihydroxy compound which can be used in the present invention,and the present invention is not limited thereto. One of these alicyclicdiol compounds may be used alone, or two or more thereof may be mixedand used.

As for the ratio between the constitutional unit derived from adihydroxy compound represented by formula (1) and the constitutionalunit derived from an alicyclic dihydroxy compound, which are containedin the polycarbonate copolymer of the present invention, the ratio maybe arbitrarily selected but is preferably constitutional unit derivedfrom a dihydroxy compound represented by formula (1): constitutionalunit derived from an alicyclic dihydroxy compound=from 1:99 to 99:1 (mol%), particularly preferably constitutional unit derived from a dihydroxycompound represented by formula (1): constitutional unit derived from analicyclic dihydroxy compound=from 10:90 to 90:10 (mol %). If theconstitutional unit derived from a dihydroxy compound represented byformula (1) exceeds this range and the constitutional unit derived froman alicyclic dihydroxy compound is less than the range above, colorationof the polycarbonate obtained readily occurs, whereas if theconstitutional unit derived from a dihydroxy compound represented byformula (1) is less than the range above and the constitutional unitderived from an alicyclic dihydroxy compound exceeds the range above,the molecular weight tends to be difficult to increase.

The polycarbonate copolymer of the present invention may contain aconstitutional unit derived from a dihydroxy compound (hereinafter,sometimes referred to as “the other dihydroxy compound”) other than thedihydroxy compound represented by formula (1) and the alicyclicdihydroxy compound. In this case, examples of the other dihydroxycompound include aliphatic dihydroxy compounds such as ethylene glycol,1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol,1,2-butanediol, 1,5-heptanediol and 1,6-hexanediol; oxyalkylene glycolssuch as diethylene glycol, triethylene glycol and tetraethylene glycol;and aromatic bisphenols such as 2,2-bis(4-hydroxyphenyl)propane[=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,2,2-bis(4-hydroxy-3,5-diethylphenyl)propane,2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)-propane,2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,2,2-bis(4-hydroxyphenyl)pentane, 2,4′-dihydroxy-diphenylmethane,bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane,1,1-bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)sulfone,2,4′-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide,4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenylether, 4,4′-dihydroxy-2,5-diethoxydiphenyl ether,9,9-bis(4-(2-hydroxyethoxy)-phenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy-2-methyl)-phenyl)fluorene,9,9-bis(4-hydroxyphenyl)fluorene, and9,9-bis(4-hydroxy-2-methylphenyl)fluorene. One member or two or moremembers thereof may be used.

Effects such as improvement of flexibility, enhancement of heatresistance and improvement of moldability may be obtained by using suchother dihydroxy compound, but if a constitutional unit derived from theother dihydroxy compound is contained in an excessively largeproportion, original optical characteristics may be deteriorated in theperformance. Therefore, in the polycarbonate copolymer of the presentinvention, the total ratio of the dihydroxy compound represented byformula (1) and the alicyclic dihydroxy compound to all dihydroxycompounds constituting the polycarbonate copolymer is preferably 90 mol% or more. In particular, the polycarbonate copolymer of the presentinvention is preferably composed of, in terms of the dihydroxy compound,only the dihydroxy compound represented by formula (1) and the alicyclicdihydroxy compound.

The polymerization degree of the polycarbonate copolymer of the presentinvention is preferably a polymerization degree such that the reducedviscosity measured at a temperature of 20.0° C.±0.1° C. by using, as thesolvent, a mixed solution of phenol and 1,1,2,2-tetrachloroethane at aweight ratio of 1:1 and precisely adjusting the polycarbonate copolymerconcentration to 1.00 g/dl (hereinafter simply referred to as a “reducedviscosity of the polycarbonate copolymer”) is 0.40 dl/g or more,particularly from 0.40 to 2.0 dl/g. If the reduced viscosity of thepolycarbonate copolymer is excessively low, the mechanical strength of alens or the like molded is weak, whereas if the reduced viscosity of thepolycarbonate copolymer becomes large, flowability at the moldingdecreases and this tends to bring about reduction in the cycle propertyand a large birefringence of the molded article. Accordingly, thereduced viscosity of the polycarbonate copolymer of the presentinvention is preferably from 0.40 to 2.0 dl/g, particularly preferablyfrom 0.45 to 1.5 dl/g.

The Abbe number of the polycarbonate copolymer of the present inventionis preferably 50 or more, particularly preferably 55 or more. As thisvalue is larger, the wavelength dispersion of the refractive indexbecomes small and, for example, in use as a single lens, chromaticaberration is reduced to facilitate obtaining a clearer image. A smallerAbbe number gives rise to a larger wavelength dispersion of therefractive index and in use as a single lens, there are caused a largerchromatic aberration and a larger blur degree of the image.

The 5% thermal reduction temperature of the polycarbonate copolymer ofthe present invention is preferably 340° C. or more, particularlypreferably 345° C. or more. As the 5% thermal reduction temperature islarger, the thermal stability increases to enable withstanding use at ahigher temperature. If this temperature becomes smaller, thermalstability decreases to hardly allow for use at a high temperature andthe copolymer is difficult to produce due to a narrow control latitudeat the production. In the range above, a high production temperature anda wider control latitude at the production are allowed and theproduction becomes easy.

The photoelastic coefficient of the polycarbonate copolymer of thepresent invention is preferably 40×10⁻¹² Pa⁻¹ or less, more preferably20×10⁻¹² Pa⁻¹ or less. If the photoelastic coefficient value is high,the film produced by melt extrusion, solution casting or the like comesto have a large phase difference value and when this film is stretched,the phase difference value in the film plane is further fluctuated dueto slight tension variation. In the case of laminating such a phasedifference film, not only the desired phase difference is misaligned bythe tension at the lamination but also the phase difference valuereadily changes due to shrinkage or the like of the polarizing plateafter lamination. As the photoelastic coefficient is smaller, thefluctuation of phase difference is more reduced.

The polycarbonate copolymer of the present invention preferably has anIzod impact strength of 30 J/m² or more. As the Izod impact strength islarger, the molded body is increased in the strength and hardly broken.

In the polycarbonate copolymer of the present invention, the amount ofthe generated gas except for a phenol component (hereinafter sometimessimply referred to as the “amount of the generated gas”) per unit areaat 110° C. is preferably 5 ng/cm² or less. Also, the amount of thegenerated gas derived from a dihydroxy compound other than the dihydroxycompound represented by formula (1) is preferably 0.5 ng/cm² or less. Asthis amount of the generated gas is smaller, the polycarbonate copolymeris more applicable to usage requiring to avoid the effect of thegenerated gas, for example, usage in storing an electronic componentsuch as semiconductor or usage as an interior material of building or asa casing for home appliances or the like.

The methods for measuring the Abbe number, 5% thermal reductiontemperature, photoelastic coefficient, Izod impact strength and amountof generated gas of the polycarbonate copolymer of the present inventionare specifically as described later in Examples.

The polycarbonate copolymer of the present invention gives a singleglass transition temperature when subjected to differential scanningcalorimetry (DSC), and the polycarbonate copolymer of the presentinvention can be obtained as a polymer having an arbitrary glasstransition temperature between about 45° C. and about 155° C. accordingto usage by adjusting the kinds and blending ratio of the dihydroxycompound represented by formula (1) and the alicyclic dihydroxycompound.

For example, in the usage as a film requiring flexibility, the glasstransition temperature of the polycarbonate copolymer is preferablyadjusted to 45° C. or more, for example, from 45 to 100° C., and in theusage as a molded body such as bottle or pack requiring heat resistanceto a certain extent, the glass transition temperature of thepolycarbonate copolymer is preferably adjusted to 90° C. or more, forexample, from 90 to 130° C. Furthermore, when the glass transitiontemperature is 120° C. or more, this is suitable for the usage as alens. That is, a lens having such a glass transition temperature ispreferred, because deformation scarcely occurs even underhigh-temperature high-humidity conditions at a temperature of 85° C. anda relative humidity of 85% and the surface accuracy of the lens is lessfluctuated.

The polycarbonate copolymer of the present invention can be produced bya generally employed polymerization method, and the polymerizationmethod may be either a solution polymerization method using phosgene ora melt polymerization method by the reaction with a carbonic aciddiester, but a melt polymerization method is preferred, where thedihydroxy compound represented by formula (1), the alicyclic dihydroxycompound and, if desired, the other dihydroxy compound are reacted witha carbonic acid diester less toxic to the environment in the presence ofa polymerization catalyst.

The carbonic acid diester usually used in this melt polymerizationmethod includes a carbonic acid diester represented by the followingformula (2):

(in formula (2), A and A′ each is an aliphatic group having a carbonnumber of 1 to 18, which may have a substituent, or an aromatic groupwhich may have a substituent, and A and A′ may be the same ordifferent).

Examples of the carbonic acid diester represented by formula (2) includediphenyl carbonate, a substituted diphenyl carbonate as typified byditolyl carbonate, dimethyl carbonate, diethyl carbonate, anddi-tert-butyl carbonate. Among these, diphenyl carbonate and asubstituted diphenyl carbonate are particularly preferred. One of thesecarbonic acid diesters may be used alone, or two or more thereof may bemixed and used.

The carbonic acid diester is preferably used in a molar ratio of 0.90 to1.10, more preferably from 0.96 to 1.04, based on all dihydroxycompounds used for the reaction. If this molar ratio is less than 0.90,the terminal OH group of the produced polycarbonate copolymer isincreased, as a result, the thermal stability of the polymer may beworsened or a polymer having a desired high molecular weight may not beobtained, whereas if this molar ratio exceeds 1.10, not only the rate ofa trans-esterification reaction decreases under the same conditions or apolycarbonate copolymer having a desired molecular weight is difficultto produce but also the amount of the residual carbonic acid diester inthe polycarbonate copolymer produced is increased and this residualcarbonic acid diester disadvantageously gives rise to an odor at themolding or of a molded article.

The ratio in which the dihydroxy compound represented by formula (1),the alicyclic dihydroxy compound and, if desired, the other dihydroxycompound are used is the same as the ratio of constituent units derivedfrom respective dihydroxy compounds constituting the polycarbonatecopolymer of the present invention, as described above.

As for the polymerization catalyst (trans-esterification catalyst) inthe melt polymerization, an alkali metal compound and/or an alkalineearth metal compound are used. Together with the alkali metal compoundand/or alkaline earth metal compound, a basic compound such as basicboron compound, basic phosphorus compound, basic ammonium compound andamine-based compound may be subsidiarily used in combination, but it isparticularly preferred to use only an alkali metal compound and/or analkaline earth metal compound.

Examples of the alkali metal compound used as the polymerizationcatalyst include sodium hydroxide, potassium hydroxide, lithiumhydroxide, cesium hydroxide, sodium hydrogencarbonate, potassiumhydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate,sodium carbonate, potassium carbonate, lithium carbonate, cesiumcarbonate, sodium acetate, potassium acetate, lithium acetate, cesiumacetate, sodium stearate, potassium stearate, lithium stearate, cesiumstearate, sodium borohydride, potassium borohydride, lithiumborohydride, cesium borohydride, sodium phenylborate, potassiumphenylborate, lithium phenylborate, cesium phenylborate, sodiumbenzoate, potassium benzoate, lithium benzoate, cesium benzoate,disodium hydrogenphosphate, dipotassium hydrogenphosphate, dilithiumhydrogenphosphate, dicesium hydrogenphosphate, disodiumhydrogenphosphite, potassium hydrogenphosphite, dilithiumhydrogenphosphite, dicesium hydrogenphosphite, disodium phenylphosphate,dipotassium phenylphosphate, dilithium phenylphosphate, dicesiumphenylphosphate, alcoholate and phenolate of sodium, potassium, lithiumand cesium, and disodium, dipotassium, dilithium and dicesium salts ofbisphenol A.

Examples of the alkaline earth metal compound include calcium hydroxide,barium hydroxide, magnesium hydroxide, strontium hydroxide, calciumhydrogencarbonate, barium hydrogencarbonate, magnesiumhydrogencarbonate, strontium hydrogencarbonate, calcium carbonate,barium carbonate, magnesium carbonate, strontium carbonate, calciumacetate, barium acetate, magnesium acetate, strontium acetate, calciumstearate, barium stearate, magnesium stearate, and strontium stearate.

One of these alkali metal compounds and/or alkaline earth metalcompounds may be used alone, or two or more thereof may be used incombination.

Specific examples of the basic boron compound which is used incombination with the alkali metal compound and/or alkaline earth metalcompound include sodium, potassium, lithium, calcium, barium, magnesiumand strontium salts of tetramethylboron, tetraethylboron,tetrapropylboron, tetrabutylboron, trimethylethylboron,trimethylbenzylboron, trimethylphenylboron, triethylmethylboron,triethylbenzylboron, triethylphenylboron, tributylbenzylboron,tributylphenylboron, tetraphenylboron, benzyltriphenylboron,methyltriphenylboron and butyltriphenylboron.

Examples of the basic phosphorus compound include triethylphosphine,tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine,triphenylphosphine, tributylphosphine, and quaternary phosphonium salt.

Examples of the basic ammonium compound include tetramethylammoniumhydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,tetrabutylammonium hydroxide, trimethylethylammonium hydroxide,trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide,triethylmethyl ammonium hydroxide, triethylbenzylammonium hydroxide,triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide,tributylphenylammonium hydroxide, tetraphenylammonium hydroxide,benzyltriphenylammonium hydroxide, methyltriphenyl ammonium hydroxide,and butyltriphenylammonium hydroxide.

Examples of the amine-based compound include 4-aminopyridine,2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylamino pyridine,2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine,2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole,2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

These basic compounds may also be used alone, or two or more thereof maybe used in combination.

As for the amount of the polymerization catalyst used, in the case ofusing an alkali metal compound and/or an alkaline earth metal compound,the polymerization catalyst is usually used, in terms of the metal, inan amount of 0.01 to 100 μmol, preferably from 0.05 to 50 μmol, morepreferably from 0.1 to 10 μmol, per mol of all dihydroxy compounds usedfor the reaction. If the amount of the polymerization catalyst used istoo small, polymerization activity necessary for producing apolycarbonate copolymer having a desired molecular weight cannot beobtained, whereas if the amount of the polymerization catalyst used isexcessively large, the color hue of the obtained polycarbonate copolymermay be worsened or a by-product may be generated to cause manyoccurrences of reduction in flowability or production of a gel, as aresult, a polycarbonate copolymer having an intended quality can behardly produced.

In producing the polycarbonate copolymer of the present invention, thedihydroxy compound represented by formula (I) may be fed as a solid, maybe heated and fed in a melted state, or may be fed in the form of anaqueous solution.

The alicyclic dihydroxy compound may also be fed as a solid, may beheated and fed in a melted state, or if soluble in water, may be fed inthe form of an aqueous solution. The same applies to the other dihydroxycompound.

When such a raw material dihydroxy compound is fed in a melted state orin the form of an aqueous solution, this is advantageous in thatweighing or transportation is facilitated at the industrial production.

In the present invention, the method of reacting the dihydroxy compoundrepresented by formula (I), the alicyclic dihydroxy compound and, ifdesired, the other dihydroxy compound with a carbonic acid diester inthe presence of a polymerization catalyst is usually performed by amulti-step process of two or more steps. Specifically, the reaction inthe first step is performed at a temperature of 140 to 240° C.,preferably from 150 to 220° C., for 0.1 to 10 hours, preferably from 0.5to 3 hours. In the second and subsequent steps, the reaction temperatureis elevated while gradually reducing the pressure of the reaction systemfrom the pressure in the first step and at the same time, removing thegenerated phenol outside of the reaction system, and thepolycondensation reaction is performed finally under a pressure in thereaction system of 200 Pa or less at a temperature of 180 to 280° C.

At the time of reducing the pressure in this polycondensation reaction,it is important to control the balance between the temperature and thepressure in the reaction system. In particular, if even either one ofthe temperature and the pressure is too rapidly changed, an unreactedmonomer is distilled out to upset the molar ratio of the dihydroxycompound to the carbonic acid diester and the polymerization degree maydecrease. For example, in the case of using isosorbide and1,4-cyclohexanedimethanol as dihydroxy compounds, when the molar ratioof 1,4-cyclohexanedimethanol is 50 mol % or more based on all dihydroxycompounds, 1,4-cyclohexanedimethanol still as a monomer is readilydistilled out. Therefore, it is preferred to perform the reaction whileelevating the temperature at a temperature rise rate of 40° C. or lessper hour under reduced pressure where the pressure in the reactionsystem is about 13 kPa, further elevate the temperature at a temperaturerise rate of 40° C. or less per hour under a pressure up to about 6.67kPa, and perform the polycondensation reaction finally under a pressureof 200 Pa or less at a temperature of 200 to 250° C., because apolycarbonate copolymer sufficiently increased in the polymerizationdegree is obtained.

Also, when the molar ratio of 1,4-cyclohexanedimethanol is reduced toless than 50 mol %, particularly mol % or less, based on all dihydroxycompounds, increase of viscosity abruptly occurs as compared with thecase of the molar ratio of 1,4-cyclohexanedimethanol being 50 mol % ormore. Therefore, it is preferred to perform the reaction while elevatingthe temperature at a temperature rise rate of 40° C. or less per houruntil the pressure in the reaction system is reduced to about 13 kPa,further perform the reaction while elevating the temperature at atemperature rise rate of 40° C. or more per hour, preferably 50° C. ormore per hour, under a pressure up to about 6.67 kPa, and perform thepolycondensation reaction finally under reduced pressure of 200 Pa orless at a temperature of 200 to 280° C., because a polycarbonatecopolymer sufficiently increased in the polymerization degree isobtained.

The reaction form may be a batch system, a continuous system, or acombination of batch system and continuous system.

In producing the polycarbonate copolymer of the present invention by amelt polymerization method, a phosphoric acid compound, a phosphorousacid compound, or a metal salt thereof may be added at thepolymerization for the purpose of preventing coloration.

As for the phosphoric acid compound, one species or two or more speciesof a trialkyl phosphate such as trimethyl phosphate and triethylphosphate are suitably used. This compound is preferably added in anamount of 0.0001 to 0.005 mol %, more preferably from 0.0003 to 0.003mol %, based on all dihydroxy compounds used for the reaction. If theamount of the phosphorus compound added is less than the lower limitabove, the effect of preventing coloration is small, whereas if itexceeds the upper limit, this may cause increase in the haze or mayconversely accelerate the coloration or decrease the heat resistance.

In the case of adding a phosphorous acid compound, the compound may bearbitrarily selected from the following thermal stabilizers. Inparticular, one member or two or more members of trimethyl phosphite,triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate,tris(2,4-di-tert-butylphenyl)phosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite may be suitablyused. The phosphorous acid compound is preferably added in an amount of0.0001 to 0.005 mol %, more preferably from 0.0003 to 0.003 mol %, basedon all dihydroxy compounds used for the reaction. If the amount of thephosphorous acid compound added is less than the lower limit above, theeffect of preventing coloration is small, whereas if it exceeds theupper limit, this may cause increase in the haze or may converselyaccelerate the coloration or decrease the heat resistance.

A phosphoric acid compound and a phosphorous acid compound or a metalsalt thereof may be used in combination and in this case, the amountadded is, in terms of the total amount of a phosphoric acid compound anda phosphorous acid compound or a metal salt thereof, is preferably from0.0001 to 0.005 mol %, more preferably from 0.0003 to 0.003 mol %, basedon all dihydroxy compounds described above. If the amount added is lessthan the lower limit above, the effect of preventing coloration issmall, whereas if it exceeds the upper limit, this may cause increase inthe haze or may conversely accelerate the coloration or decrease theheat resistance.

The metal salt of a phosphoric acid compound or phosphorous acidcompound is preferably a zinc salt, and among zinc phosphates, a zinclong-chain alkylphosphate such as zinc stearylphosphate is preferred.

In the thus-produced polycarbonate copolymer of the present invention, athermal stabilizer may be blended so as to prevent reduction in themolecular weight or worsening of the color hue at the molding or thelike.

Examples of the thermal stabilizer include a phosphorous acid, aphosphoric acid, a phosphonous acid, a phosphonic acid, and an esterthereof. Specific examples thereof include triphenyl phosphite,tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite,tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite,didecylmonophenyl phosphite, dioctylmonophenyl phosphite,diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite,monodecyldiphenyl phosphite, monooctyldiphenyl phosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite,bis(nonylphenyl)pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,distearylpentaerythritol diphosphite, tributyl phosphate, triethylphosphate, trimethyl phosphate, triphenyl phosphate,diphenylmonoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate,diisopropyl phosphate, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphinate, dimethyl benzenephosphonate, diethylbenzenephosphonate, and dipropyl benzenephosphonate. Among these,preferred are trisnonylphenyl phosphite, trimethyl phosphate,tris(2,4-di-tert-butylphenyl)phosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, anddimethyl benzenephosphonate.

One of these thermal stabilizers may be used alone, or two or morethereof may be used in combination.

The thermal stabilizer may be further additionally blended in additionto the amount added at the melt polymerization. More specifically, whena polycarbonate copolymer is obtained by blending an appropriate amountof a phosphorous acid compound or phosphoric acid compound andthereafter, a phosphorous acid compound is further blended by theblending method described later, a large amount of a heat stabilizer canbe blended while avoiding increase in the haze, coloration and reductionin the heat resistance at the polymerization, and the color hue can beprevented from worsening.

The blending amount of the thermal stabilizer is preferably from 0.0001to 1 part by weight, more preferably from 0.0005 to 0.5 parts by weight,still more preferably from 0.001 to 0.2 parts by weight, per 100 partsby weight of the polycarbonate copolymer.

In the polycarbonate copolymer of the present invention, a generallyknown antioxidant may also be blended for the purpose of preventingoxidation.

Examples of the antioxidant include pentaerythritoltetrakis(3-mercaptopropionate), pentaerythritoltetrakis(3-laurylthiopropionate), glycerol-3-stearyl-thiopropionate,triethyleneglycol-bis([3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,N,N-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide),3,5-di-tert-butyl-4-hydroxy-benzyl phosphonate-diethyl ester,tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphinate, and3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.One of these antioxidants or two or more thereof may be used.

The blending amount of the antioxidant is preferably from 0.0001 to 0.5parts by weight per 100 parts by weight of the polycarbonate.

In the polycarbonate copolymer of the present invention, for moreenhancing the releasability from a mold at the melt molding, a releasingagent may also be blended within the range not impairing the purpose ofthe present invention.

Examples of the releasing agent include a higher fatty acid ester of amonohydric or polyhydric alcohol, a higher fatty acid, paraffin wax,beeswax, an olefin-based wax, an olefin-based wax containing a carboxygroup and/or a carboxy anhydride group, silicone oil, andorgano-polysiloxane.

The higher fatty acid ester is preferably a partial or full ester of amonohydric or polyhydric alcohol having a carbon number of 1 to 20 and asaturated fatty acid having a carbon number of 10 to 30. Examples of thepartial or full ester of a monohydric or polyhydric alcohol and asaturated fatty acid include monoglyceride stearate, diglyceridestearate, triglyceride stearate, monosorbitate stearate, stearylstearate, monoglyceride behenate, behenyl behenate, pentaerythritolmonostearate, pentaerythritol tetrastearate, pentaerythritoltetrapelargonate, propylene glycol monostearate, stearyl stearate,palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate,biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate.

Among these, preferred are monoglyceride stearate, triglyceridestearate, pentaerythritol tetrastearate, and behenyl behenate.

The higher fatty acid is preferably a saturated fatty acid having acarbon number of 10 to 30. Examples of the fatty acid include myristicacid, lauric acid, palmitic acid, stearic acid, and behenic acid.

One of these releasing agents may be used alone, or two or more thereofmay be mixed and used.

The blending amount of the releasing agent is preferably from 0.01 to 5parts by weight per 100 parts by weight of the polycarbonate.

In the polycarbonate copolymer of the present invention, a lightstabilizer may also be blended within the range not impairing thepurpose of the present invention.

Examples of the light stabilizer include2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole,2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole,2-(5-methyl-2-hydroxyphenyl)benzotriazole,2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole,2,2′-methylenebis(4-cumyl-6-benzotriazolephenyl), and2,2′-p-phenylenebis(1,3-benzoxazin-4-one).

One of these light stabilizers may be used alone, or two or more thereofmay be used in combination.

The blending amount of the light stabilizer is preferably from 0.01 to 2parts by weight per 100 parts by weight of the polycarbonate copolymer.

In the polycarbonate copolymer of the present invention, a bluing agentmay be blended so as to cancel the yellow tint of the lens attributableto the polymer or ultraviolet absorbent. As for the bluing agent, abluing agent employed for polycarbonate resins may be used without anyproblem. In general, an anthraquinone-based dye is easily available andpreferred.

Specific representative examples of the bluing agent include SolventViolet 13, generic name [CA. No. (Color index No.) 60725], SolventViolet 31, generic name [CA. No. 68210], Solvent Violet 33, generic name[CA. No. 60725], Solvent Blue 94, generic name [CA. No. 61500], SolventViolet 36, generic name [CA. No. 68210], Solvent Blue 97, generic name[produced by Bayer A G, “MACROLEX VIOLET RR”], and Solvent Blue 45,generic name [CA. No. 61110].

One of these bluing agents may be used alone, or two or more thereof maybe used in combination.

The bluing agent is usually blended in a ratio of 0.1×10⁻⁴ to 2×10⁻⁴parts by weight per 100 parts by weight of the polycarbonate copolymer.

Examples of the method for blending various additives described abovewith the polycarbonate copolymer of the present invention include amethod of mixing these components by a tumbler, a V-blender, a supermixer, Nauta Mixer, a Banbury mixer, a kneading roll or an extruder, anda solution blending method of mixing respective components in a state ofbeing dissolved in a common good solvent such as methylene chloride, butthe method is not particularly limited and any method may be used aslong as it is a generally employed polymer blending method.

The thus-obtained polycarbonate copolymer of the present invention orthe polycarbonate copolymer composition prepared by adding variousadditives thereto can be formed into a molded product by a generallyknown method such as injection molding method, extrusion molding methodor compression molding method, directly or after once prepared aspellets by a melt extruder.

In order to obtain stable releasability and physical properties byincreasing the miscibility of the polycarbonate copolymer of the presentinvention, a single-screw extruder or a twin-screw extruder ispreferably used in the melt extrusion. The method using a single-screwextruder or a twin-screw extruder does not use a solvent or the like,less imposes a load on the environment and can be suitably used also inview of productivity.

The melt kneading temperature of the extruder depends on the glasstransition temperature of the polycarbonate copolymer of the presentinvention, and when the glass transition temperature of thepolycarbonate copolymer of the present invention is less than 90° C.,the melt kneading temperature of the extruder is usually from 130 to250° C., preferably from 150 to 240° C. If the melt kneading temperatureis less than 130° C., the melt viscosity of the polycarbonate copolymeris high to impose a large load on the extruder and the productivitydecreases, whereas if it exceeds 250° C., the melt viscosity of thepolycarbonate copolymer is low and preparation of pellets becomesdifficult, as a result, the productivity decreases.

Also, when the glass transition temperature of the polycarbonatecopolymer of the present invention is 90° C. or more, the melt kneadingtemperature of the extruder is usually from 200 to 300° C., preferablyfrom 220 to 260° C. If the melt kneading temperature is less than 200°C., the melt viscosity of the polycarbonate copolymer is high to imposea large load on the extruder and the productivity decreases, whereas ifit exceeds 300° C., the polycarbonate copolymer readily deteriorates andmay undergo yellowing or the molecular weight decreases to causedeterioration of the strength.

In the case of using an extruder, a filter is preferably disposed so asto prevent burning of the polycarbonate copolymer or intermingling offoreign matters at the extrusion. The pore size (opening) of the filterfor removing foreign matters varies depending on the required opticalaccuracy but is preferably 100 μm or less. In particular, when it isrequired to avoid intermingling of foreign matters, the size is morepreferably 40 μm or less, still more preferably 10 μm or less.

The extrusion of the polycarbonate copolymer is preferably performed ina clean room so as to prevent intermingling of foreign matters after theextrusion.

At the time of cooling and chipping the extruded polycarbonatecopolymer, a cooling method such as air cooling or water cooling ispreferably used. As for the air used in air cooling, air afterpreviously removing foreign materials in the air through a hepafilter orthe like is preferably used to prevent reattachment of foreign mattersin air. In the case of using water cooling, water after removing metalportions in the water by an ion-exchange resin or the like and furtherremoving foreign matters in the water through a filter is preferablyused. The filter used may have various pore sizes (openings), but afilter of 10 to 0.45 μm is preferred.

In shaping a lens by using the polycarbonate copolymer of the presentinvention, an injection molding machine or an injection compressionmolding machine is suitably used and as for the molding conditions, amold surface temperature and a resin temperature are particularlyimportant. These molding conditions vary depending on the composition,polymerization degree or the like of the polycarbonate copolymer andcannot be indiscriminately specified, but the mold surface temperatureis preferably from 30 to 170° C. and at this time, the resin temperatureis preferably set to be from 220 to 290° C. If the mold surfacetemperature is 30° C. or less, both flowability and transferability ofthe resin are bad and due to stress-strain remaining at the injectionmolding, the birefringence tends to become large, whereas if the moldtemperature is 170° C. or more, deformation readily occurs at releasing,despite good transferability. Also, if the resin temperature is 290° C.or more, decomposition of the resin readily occurs, giving rise toreduction in the strength or coloration of the molded article.Furthermore, the molding cycle is prolonged and this is not profitable.

In the case of shaping an optical material or an optical component fromthe polycarbonate copolymer of the present invention, the raw materialcharging step, the polymerization step, and the step of forming theobtained copolymer into a pellet or a sheet by extruding it in a coolingmedium are preferably performed with care not to allow for entering ofdusts and the like. The cleanliness is usually class 1,000 or less inshaping a normal compact disc, and further class 100 or less when thedisc is for high-level information recording.

The polycarbonate copolymer of the present invention may also be used asa polymer alloy by kneading it with, for example, a synthetic resin suchas aromatic polycarbonate, aromatic polyester, aliphatic polyester,polyamide, polystyrene, polyolefin, acryl, amorphous polyolefin, ABS andAS, a biodegradable resin such as polylactic acid and polybutylenesuccinate, or rubber.

The present invention is described in greater detail below by referringto Examples, but the present invention is not limited to the followingExamples as long as the gist of the invention is observed.

In Examples below, the physical properties or characteristics of thepolycarbonate copolymer were evaluated by the following methods.

(1) Refractive Index and Abbe Number

The refractive index, nC, nD, ne and nF at each wavelength were measuredby an Abbe refractometer (“DR-M4” manufactured by Atago Co., Ltd.) byusing an interference filter at a wavelength of 656 nm (C line), 589 nm(d line), 546 nm (e line) or 486 nm (F line).

A sample for measurement was prepared by press-molding a resin at atemperature of 160 to 200° C. to produce a film having a thickness of 80to 500 μm and cutting the obtained film into a rectangular form having awidth of about 8 mm and a length of 10 to 40 mm, and this sample wasused as the test specimen for measurement.

The measurement was performed at 20° C. by using 1-bromonaphthalene asthe interfacial solution.

The Abbe number νd was calculated according to the following formula:

νd=(1−nD)/(nC−nF)

As the Abbe number is larger, the wavelength dependency of therefractive index is smaller and, for example, in use as a single lens,the displacement of the focus point depending on the wavelength isreduced.

(2) Glass Transition Temperature (Tig)

Using a differential scanning calorimeter (“DSC822” manufactured byMettler), about 10 mg of the sample was heated at a temperature riserate of 10° C./min and measured to determine an extrapolation glasstransition initiating temperature Tig according to JIS K 7121 (1987),which is a temperature at an intersection between a straight line drawnby extending the base line on the low temperature side to the hightemperature side and a broken line drawn on points of giving a maximumgradient of the curve in the portion having a stepwise change of glasstransition.

(3) Color

The chip color was measured using a color meter (“300A”, manufactured byNippon Denshoku Industries Co., Ltd.). A predetermined amount of chipswere charged into a glass cell and measured by reflection measurement,and the b value was determined. As this numerical value is closer to 0,the yellow tint is weaker.

(4) Reduced Viscosity

In an automatic viscometer Model DT-504 manufactured by Chuo Rika usinga Ubbelohde viscometer, a 1:1 mixed solvent of phenol and1,1,2,2-tetrachloroethane was used as the solvent and the measurementwas performed at a temperature of 20.0° C.±0.1° C. The concentration wasprecisely adjusted to 1.00 g/dl.

The sample was dissolved over 30 minutes with stirring at 120° C. andafter cooling, used for the measurement. From the transit time t0 ofsolvent and the transit time t of solution, the relative viscosity ηrelwas calculated:

ηrel=t/t0(g·cm⁻¹·.sec⁻¹)

and from the relative viscosity ηrel, the specific viscosity ηsp wasdetermined:

ηsp=(η−η0)/η0 32 ηrel−1

The reduced viscosity (converted viscosity) ηred was determined bydividing the specific viscosity ηsp by the concentration c g/dl:

ηred=ηsp/c

As this numerical value is larger, the molecular weight is higher.

(5) 5% Thermal Reduction Temperature

Using “TG-DTA” (SSC-5200, TG/DTA220) manufactured by Seiko Instruments &Electronics Ltd., 10 mg of the sample was placed on an aluminum-madevessel and measured in a range from 30 to 450° C. at a temperature riserate of 10° C./min in an nitrogen atmosphere (flow rate of nitrogen: 200ml/min), and the temperature at which the weight was 5% reduced wasdetermined.

As this temperature is higher, thermal decomposition less occurs.

(6) Izod Impact Strength

A test specimen having a length of 31.5 mm, a width of 6.2 mm and athickness of 3.2 mm was injection-molded at a temperature of 240 to 300°C. by using a minimax injection molding machine “CS-183MMX” manufacturedby Custom Scientific and notched to a depth of 1.2 mm by a notchingmachine.

This test specimen was measured for the notched Izod impact strength at23° C. by using a minimax Izod impact tester “Model CS-183TI”manufactured by Custom Scientific.

As this value is larger, the impact strength is higher and breaking lessoccurs.

(7) Tensile Test

A tensile test specimen having a parallel part length of 9 mm and aparallel part diameter of 1.5 mm was injection-molded at a temperatureof 240 to 300° C. by using the injection molding machine above, and atensile test was performed under the condition of a tensile speed of 1cm/min by using a tensile tester “Model CS-183TE” manufactured by CustomScientific. The elongation at yield, tensile yield strength, tensileyield modulus and elongation at break were measured.

As each numerical value is larger, the strength is higher and theelongation is longer.

(8) NMR

Using deuterated chloroform as the solvent, ¹H-NMR was measured at aresonant frequency of 500 MHz, a flip angle of 45° and a measurementtemperature of 25° C. by “Unity Inova” manufactured by Varian.

(9) Photoelastic Coefficient <Production of Sample>

A polycarbonate resin sample (4.0 g) vacuum-dried at 80° C. for 5 hourswas pressed by a hot press at a hot press temperature of 200 to 250° C.for 1 minute under the conditions of a preheating for 1 to 3 minutes anda pressure of 20 MPa by using a spacer having a width of 8 cm, a lengthof 8 cm and a thickness of 0.5 mm, and then the sample with the spacerwas taken out and press-cooled by a water-tube cooling press under apressure of 20 MPa for 3 minutes to produce a sheet. A sample of 5 mm inwidth and 20 mm in length was cut out from the sheet.

<Measurement>

The measurement was performed using an apparatus combining abirefringence measuring apparatus composed of a He—Ne laser, apolarizer, a compensation plate, an analyzer and a photodetector with avibration-type viscoelasticity measuring apparatus (DVE-3, manufacturedby Rheology) (for details, see Journal of the Society of Rheology Japan,Vol. 19, pp. 93-97 (1991)).

The sample cut out was fixed in the viscoelasticity measuring apparatus,and the storage modulus E′ was measured at a room temperature of 25° C.at a frequency of 96 Hz. At the same time, laser light emitted waspassed through the polarizer, the sample, the compensation plate and theanalyzer in this order and collected in the photodetector (photodiode).With respect to the waveform at an angular frequency of ω or 2ω, phasedifference for the amplitude and strain was determined through a lock-inamplifier, and the strain-optical coefficient O′ was determined. At thistime, the directions of the polarizer and the analyzer were crossing ata right angle and each was adjusted to make an angle of π/4 with theextension direction of the sample.

The photoelastic coefficient C was determined using the storage modulusE′ and the strain-optical coefficient O′ according to the followingformula:

C=O′/E′

(10) Amount of Generated Gas <Production of Sample>

A polycarbonate resin sample (8 g) vacuum-dried at 100° C. for 5 hourswas pressed by a hot press at a hot press temperature of 200 to 250° C.for 1 minute under the conditions of a preheating for 1 to 3 minutes anda pressure of 20 MPa by using a spacer having a width of 8 cm, a lengthof 8 cm and a thickness of 0.5 mm, and then the sample with the spacerwas taken out and press-cooled by a water-tube cooling press under apressure of 20 MPa for 3 minutes to produce a sheet. A sample of 1 cm inwidth and 2 cm in length was cut out from the sheet. The thickness was 1mm.

<Measurement>

The generated gas was measured by thermal desorption-gaschromatography/mass spectrometry (TDS-GC/MS). The measuring apparatusused was TDS2 manufactured by GERSTEL, and the measurement was performedunder the conditions of a thermal desorption temperature of 250° C., 10minutes and a trap temperature of −130° C.

The sample was placed in a glass chamber and the gas generated at 110°C. for 30 minutes with helium at 60 mL/min was collected in a collectiontube Tenax-TA.

Using HP6890/5973N manufactured by Agilent as the GC/MS and using HP-VOCof 0.32×60 m and 1.8 μmdf as the column, the measurement was performed,where the temperature was kept at 40° C. for 5 minutes, then elevated to280° C. at 8° C./min, and kept at 280° C. for 25 minutes. In themeasurement, helium at 1.3 mL/min was used as the carrier gas.

The gas yield was determined in terms of toluene as the total gas yieldper unit area excluding phenol and phenol-derived benzaldehyde distilledout at the production.

(11) Pencil Hardness

A surface meter, TRIBOGEAR Type 14DR, manufactured by Shinto ScientificCo., Ltd. was used as the measuring apparatus, and the measurement wasperformed in accordance with JIS-K5600.

-   Load: 750 g-   Measuring speed: 30 mm/min-   Measuring distance: 7 mm

As the pencil, UNI produced by Mitsubishi Pencil Co., Ltd. was used.

As for the pencil hardness, 4H, 3H, 2H, H, F, HB, B, 2B, 3B and 4B wereused.

Measurement was performed 5 times, and the hardness one rank softer thanthe pencil hardness causing occurrence of scratching two or more timeswas used as the pencil hardness of the material measured.

(12) Quantitative Determination of Formic Acid

Isosorbide was 100-fold diluted with pure water and measured by an ionchromatograph Model DX-500 manufactured by Dionexy.

Incidentally, isosorbide used for the reaction was produced by RoquetteFreres and Sanko Chemical Co., Ltd., 1,4-cyclohexanedimethanol wasproduced by Eastman, cesium carbonate was produced by Wako Pure ChemicalIndustries, Ltd., diphenyl carbonate was produced by Mitsubishi ChemicalCorp., tricyclodecanedimethanol was produced by Celanese Corp.,pentacyclodecanedimethanol was produced by Celanese Corp.,1,3-adamantanediol was produced by Aldrich K.K., 1,4-butanediol wasproduced by Mitsubishi Chemical Corp., 1,6-hexanediol was produced byWako Pure Chemical Industries, Ltd., and9,9-bis-(4-(2-hydroxyethoxy)phenyl)-fluorene was produced by Osaka GasChemicals Co., Ltd.

Also, abbreviations of the compounds used in Examples are as follows.

-   ISOB: isosorbide-   1,4-CHDM: 1,4-cyclohexanedimethanol-   TCDDM: tricyclodecanedimethanol-   PCPDM: pentacyclopentadecanedimethanol-   1,4-BG: 1,4-butanediol-   1,6-HD: 1,6-hexanediol-   BHEPF: 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene-   BCF: 9,9-biscresolfluorene-   DPC: diphenyl carbonate

EXAMPLE 1

Into a reaction vessel, 13.0 parts by weight (0.246 mol) of1,4-cyclohexanedimethanol (hereinafter simply referred to as“1,4-CHDM”), 59.2 parts by weight (0.752 mol) of diphenyl carbonate(hereinafter simply referred to as “DPC”) and 2.21×10⁻⁴ parts by weight(1.84×10⁻⁶ mol) of cesium carbonate as a catalyst were charged per 27.7parts by weight (0.516 mol) of isosorbide. As a first step of thereaction, these raw materials were dissolved under heating at a heatingbath temperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 15 minutes).

Subsequently, the pressure was adjusted from normal pressure to 13.3 kPaand while elevating the heating bath temperature to 190° C. over 1 hour,the generated phenol was extracted outside of the reaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 6.67kPa, the heating bath temperature was elevated to 230° C. over 15minutes, and the generated phenol was extracted outside of the reactionvessel. With an increase in the stirring torque of the stirring machine,the temperature was elevated to 250° C. over 8 minutes, and the pressurein the reaction vessel was allowed to reach 0.200 kPa or less so as tofurther remove the generated phenol. After reaching a predeterminedstirring torque, the reaction was completed, and the reaction productproduced was extruded into water to obtain pellets of a polycarbonatecopolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 1.007dl/g, the glass transition temperature Tig was 124° C., and the color bvalue was 8.8. These results are shown in Table 1.

This polycarbonate copolymer was molded at 245° C. and a moldtemperature of 90° C. to obtain a test specimen having a length of 31.5mm, a width of 6.2 mm and a thickness of 3.2 mm and a tensile testspecimen having a parallel part length of 9 mm and a parallel partdiameter of 1.5 mm. Using these test specimens, evaluation of mechanicalproperties was performed, as a result, the tensile yield strength was 84MPa, the tensile yield modulus was 748 MPa, the elongation at yield was16%, the elongation at break was 30%, and the Izod impact strength was227 J/m². These results are shown in Table 2.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.4992 and the Abbe number was 58. These resultsare shown in Table 3.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 344° C. This result is shown in Table 4.

Furthermore, the amount of the generated gas was examined, as a result,the amount of the generated gas other than the phenol component was 3.7ng/cm² and a generated gas derived from dihydroxy compounds excludingthe dihydroxy compound represented by formula (1) was not detected.These results are shown in Table 6.

FIG. 1 shows the NMR chart of this polycarbonate copolymer.

EXAMPLE 2

Into a reaction vessel, 31.8 parts by weight (0.458 mol) of isosorbide,8.7 parts by weight (0.127 mol) of 1,4-CHDM, 59.5 parts by weight (0.583mol) of DPC and 2.22×10⁻⁴ parts by weight (1.43×10⁻⁶ mol) of cesiumcarbonate as a catalyst were charged. As a first step of the reaction,these raw materials were dissolved under heating at a heating bathtemperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 15 minutes).

Subsequently, the pressure was adjusted from normal pressure to 13.3 kPaand while elevating the heating bath temperature to 190° C. over 1 hour,the generated phenol was extracted outside of the reaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 6.67kPa, the heating bath temperature was elevated to 240° C. over 20minutes, and the generated phenol was extracted outside of the reactionvessel. With an increase in the stirring torque of the stirring machine,the pressure in the reaction vessel was allowed to reach 0.200 kPa orless so as to further remove the generated phenol. After reaching apredetermined stirring torque, the reaction was completed, and thereaction product produced was extruded into water to obtain pellets of apolycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.757dl/g, the glass transition temperature Tig was 133° C., and the color bvalue was 8.2. These results are shown in Table 1.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 the refractive indexfor d line was 1.5004 and the Abbe number was 57. These results areshown in Table 3.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 343° C. This result is shown in Table 4.

Furthermore, the photoelastic coefficient was measured and found to be20×10⁻¹² Pa⁻¹. This result is shown in Table 5 together with the valueof the glass transition temperature.

EXAMPLE 3

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 35.9 parts by weight (0.674 mol) ofisosorbide, 4.4 parts by weight (0.083 mol) of 1,4-CHDM, 59.7 parts byweight (0.764 mol) of DPC and 2.22×10⁻⁴ parts by weight (1.87×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.712dl/g, the glass transition temperature Tig was 148° C., and the color bvalue was 9.1. These results are shown in Table 1.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.5014 and the Abbe number was 57. These resultsare shown in Table 3.

EXAMPLE 4

The reaction was performed in the same manner as in Example 1 except forchanging the raw materials to 19.7 parts by weight (0.363 mol) ofisosorbide, 21.6 parts by weight (0.404 mol) of 1,4-CHDM, 58.8 parts byweight (0.741 mol) of DPC and 2.19×10⁻⁴ parts by weight (1.82×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 1.196dl/g, the glass transition temperature Tig was 101° C., and the color bvalue was 7.7. These results are shown in Table 1.

This polycarbonate copolymer was molded at a temperature of 245° C. anda mold temperature of 80° C. to obtain a test specimen having a lengthof 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm and a tensiletest specimen having a parallel part length of 9 mm and a parallel partdiameter of 1.5 mm. Using these test specimens, evaluation of mechanicalproperties was performed, as a result, the tensile yield strength was 66MPa, the tensile yield modulus was 595 MPa, the elongation at yield was16%, the elongation at break was 27%, and the Izod impact strength was293 J/m². These results are shown in Table 2.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.4993 and the Abbe number was 61. These resultsare shown in Table 3.

Furthermore, the 5% thermal reduction temperature of the polycarbonatecopolymer in a nitrogen atmosphere was 345° C. This result is shown inTable 4.

EXAMPLE 5

Into a reaction vessel, 25.8 parts by weight (0.480 mol) of 1,4-CHDM,58.6 parts by weight (0.734 mol) of DPC and 2.18×10⁻⁴ parts by weight(1.80×10⁻⁶ mol) of cesium carbonate as a catalyst were charged per 15.7parts by weight (0.288 mol) of isosorbide. As a first step of thereaction, these raw materials were dissolved under heating at a heatingbath temperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 15 minutes).

Subsequently, the pressure was adjusted from normal pressure to 13.3 kPaand while elevating the heating bath temperature to 190° C. over 1 hour,the generated phenol was extracted outside of the reaction vessel. Afterkeeping at 190° C. for 30 minutes, as a second step, the pressure in thereaction vessel was adjusted to 6.67 kPa, the heating bath temperaturewas elevated to 240° C. over 45 minutes, and the generated phenol wasextracted outside of the reaction vessel. With an increase in thestirring torque of the stirring machine, the pressure in the reactionvessel was allowed to reach 0.200 kPa or less so as to further removethe generated phenol. After reaching a predetermined stirring torque,the reaction was completed, and the reaction product produced wasextruded into water to obtain pellets.

The reduced viscosity of the obtained polycarbonate copolymer was 1.186dl/g, the glass transition temperature Tig was 89° C., and the color bvalue was 5.1. These results are shown in Table 1.

This polycarbonate copolymer was molded at a temperature of 245° C. anda mold temperature of 70° C. to obtain a test specimen having a lengthof 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm and a tensiletest specimen having a parallel part length of 9 mm and a parallel partdiameter of 1.5 mm. Using these test specimens, evaluation of mechanicalproperties was performed, as a result, the tensile yield strength was 59MPa, the tensile yield modulus was 541 MPa, the elongation at yield was15%, the elongation at break was 70%, and the Izod impact strength was784 J/m². These results are shown in Table 2.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.4993 and the Abbe number was 62. These resultsare shown in Table 3.

EXAMPLE 6

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 27.7 parts by weight (0.516 mol) ofisosorbide, 13.0 parts by weight (0.246 mol) of 1,4-CHDM, 59.2 parts byweight (0.752 mol) of DPC and 2.21×10⁻⁴ parts by weight (1.84×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.979dl/g, the glass transition temperature Tig was 124° C., and the color bvalue was 9.5. These results are shown in Table 1.

This polycarbonate copolymer was molded at a temperature of 245° C. anda mold temperature of 90° C. to obtain a test specimen having a lengthof 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm and a tensiletest specimen having a parallel part length of 9 mm and a parallel partdiameter of 1.5 mm. Using these test specimens, evaluation of mechanicalproperties was performed, as a result, the tensile yield strength was 78MPa, the tensile yield modulus was 691 MPa, the elongation at yield was16%, the elongation at break was 47%, and the Izod impact strength was184 J/m². These results are shown in Table 2.

Also, the pencil hardness was H. This result is shown in Table 7.

EXAMPLE 7

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 27.7 parts by weight (0.516 mol) ofisosorbide, 13.0 parts by weight (0.246 mol) of 1,4-CHDM, 59.2 parts byweight (0.752 mol) of DPC and 8.7×10⁻⁵ parts by weight (5.9×10⁻⁶ mol) ofsodium hydroxide as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.965dl/g, the glass transition temperature Tig was 123° C., and the color bvalue was 9.4. These results are shown in Table 1.

EXAMPLE 8

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 28.2 parts by weight (0.516 mol) ofisosorbide, 13.3 parts by weight (0.246 mol) of 1,4-CHDM, 58.5 parts byweight (0.730 mol) of DPC and 2.25×10⁻⁴ parts by weight (1.84×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.496dl/g, the glass transition temperature Tig was 122° C., and the color bvalue was 9.6. These results are shown in Table 1.

Also, the pencil hardness was H. This result is shown in Table 7.

EXAMPLE 9

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 27.7 parts by weight (0.516 mol) ofisosorbide, 13.0 parts by weight (0.246 mol) of 1,4-CHDM, 59.2 parts byweight (0.752 mol) of DPC and 2.21×10⁻⁵ parts by weight (1.84×10⁻⁷ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.910dl/g, the glass transition temperature Tig was 124° C., and the color bvalue was 9.8. These results are shown in Table 1.

EXAMPLE 10

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 27.7 parts by weight (0.516 mol) ofisosorbide, 13.0 parts by weight (0.246 mol) of 1,4-CHDM, 59.2 parts byweight (0.752 mol) of DPC and 2.21×10⁻³ parts by weight (1.84×10⁻⁵ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.980dl/g, the glass transition temperature Tig was 124° C., and the color bvalue was 8.3. These results are shown in Table 1.

EXAMPLE 11

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 27.7 parts by weight (0.516 mol) ofisosorbide, 13.0 parts by weight (0.246 mol) of 1,4-CHDM and 59.2 partsby weight (0.752 mol) of DPC and performing the polymerization bycharging, together with the raw materials, 0.096 parts by weight of athermal stabilizer “PEP-36”(bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,produced by Asahi Denka Co., Ltd.) into the reaction vessel.

The reduced viscosity of the obtained polycarbonate copolymer was 0.975dl/g, the glass transition temperature Tig was 124° C., and the color bvalue was 7.2. These results are shown in Table 1.

EXAMPLE 12

The reaction was performed in the same manner as in Example 2 except forchanging the raw materials to 19.7 parts by weight (0.363 mol) ofisosorbide, 21.6 parts by weight (0.404 mol) of 1,4-CHDM, 58.8 parts byweight (0.741 mol) of DPC and 2.19×10⁻⁴ parts by weight (1.82×10⁻⁶ mol)of cesium carbonate as a catalyst and performing the polymerization bycharging, together with the raw materials, 0.096 parts by weight of athermal stabilizer “PEP-36”(bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,produced by Asahi Denka Co., Ltd.) into the reaction vessel.

The reduced viscosity of the obtained polycarbonate copolymer was 0.850dl/g, the glass transition temperature Tig was 100° C., and the color bvalue was 3.6. These results are shown in Table 1.

COMPARATIVE EXAMPLE 1

Into a reaction vessel, 59.9 parts by weight (0.592 mol) of DPC and2.23×10⁻⁴ parts by weight (1.45×10⁻⁶ mol) of cesium carbonate as acatalyst were charged per 40.1 parts by weight (0.581 mol) ofisosorbide. These raw materials were dissolved under heating from roomtemperature to 150° C. while stirring (about 15 minutes).

Subsequently, the pressure was adjusted from normal pressure to 13.3 kPaand while elevating the temperature to 190° C. over 1 hour, thegenerated phenol was extracted outside of the system. After keeping at190° C. for 15 minutes, the pressure in the reaction vessel was adjustedto 6.67 kPa, the heating bath temperature was elevated to 230° C. over15 minutes, and the generated phenol was extracted. With an increase inthe stirring torque, the temperature was elevated to 250° C. over 8minutes, and the degree of vacuum was allowed to reach 0.200 kPa or lessso as to further remove the generated phenol. After reaching apredetermined stirring torque, the reaction was completed and extrusionof the reaction product into water to obtain pellets was tried, butsince this failed, the reaction product was taken out in the form of alump.

The reduced viscosity of the obtained polycarbonate copolymer was 0.679dl/g, the glass transition temperature was 160° C., and the color bvalue was 13.0. The b value was high as compared with Examples and thecopolymer was colored brown. These results are shown in Table 1.

This polycarbonate copolymer was molded at 265° C. by trying to sample atest specimen having a length of 31.5 mm, a width of 6.2 mm and athickness of 3.2 mm and a tensile test specimen having a parallel partlength of 9 mm and a parallel part diameter of 1.5 mm, but there wereencountered problems of high melt viscosity, intense coloration,vigorous foaming and bad yield of a molded article. Using these testspecimens, evaluation of mechanical properties was performed, as aresult, the tensile yield strength was 105 MPa, the tensile yieldmodulus was 353 MPa, the elongation at yield was 17%, the elongation atbreak was 31%, and the Izod impact strength was 11 J/m². The Izod impactstrength was found to be extremely low as compared with Examples. Theseresults are shown in Table 2.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 339° C. and was found to be low as compared withExamples. This result is shown in Table 4.

Also, this polycarbonate copolymer was pressed at 200° C. to obtain afilm having a thickness of about 200 μm. The obtained film was crackedwhen cut with scissors and brittle.

COMPARATIVE EXAMPLE 2

Into a reaction vessel, 42.3 parts by weight (0.776 mol) of 1,4-CHDM,57.7 parts by weight (0.712 mol) of DPC and 2.15×10⁻⁴ parts by weight(1.75×10⁻⁶ mol) of cesium carbonate as a catalyst were charged. As afirst step of the reaction, these raw materials were dissolved underheating at a heating bath temperature of 150° C. while stirring, ifdesired, in a nitrogen atmosphere (about 15 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 3 minutes and this pressure was kept. While elevating the heatingbath temperature to 190° C. over 60 minutes, the generated phenol wasextracted outside of the reaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 6.67kPa, the heating bath temperature was elevated to 220° C. over 45minutes, and the generated phenol was extracted out of the reactionvessel. With an increase in the stirring torque of the stirring machine,the pressure in the reaction vessel was allowed to reach 0.200 kPa orless so as to further remove the generated phenol. After reaching apredetermined stirring torque, the reaction was completed and thereaction product produced was extruded into water to obtain pellets of apolycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.662dl/g, the glass transition temperature was 40° C., and the color b valuewas 4.5. Because of the low glass transition temperature, the pelletsaggregated together and could be hardly chipped. These results are shownin Table 1.

COMPARATIVE EXAMPLE 3

A commercially available aromatic polycarbonate resin “Iupilon H4000”(produced by Mitsubishi Engineering-Plastics Corporation, reducedviscosity: 0.456 dl/g) was molded at 280° C. to obtain a test specimenhaving a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mmand a tensile test specimen having a parallel part length of 9 mm and aparallel part diameter of 1.5 mm.

Using these test specimens, evaluation of mechanical properties wasperformed, as a result, the tensile yield strength was 63 MPa, thetensile yield modulus was 629 MPa, the elongation at yield was 13%, theelongation at break was 74%, and the Izod impact strength was 6 J/m².These results are shown in Table 2.

Also, this aromatic polycarbonate resin was pressed at 200° C. to obtaina film having a thickness of about 200 μm. The refractive index for dline was 1.5828 and the Abbe number was 30. These results are shown inTable 3.

Furthermore, the photoelastic coefficient was measured and found to be72×10⁻¹² Pa⁻¹. This result is shown in Table 5 together with the valueof the glass transition temperature.

In addition, the pencil hardness was 2B. This result is shown in Table7.

COMPARATIVE EXAMPLE 4

A commercially available aromatic polycarbonate resin “Iupilon S2000”(produced by Mitsubishi Engineering-Plastics Corporation, reducedviscosity: 0.507 dl/g) was molded at 280° C. to obtain a test specimenhaving a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mmand a tensile test specimen having a parallel part length of 9 mm and aparallel part diameter of 1.5 mm.

Using these test specimens, evaluation of mechanical properties wasperformed, as a result, the tensile yield strength was 63 MPa, thetensile yield modulus was 565 MPa, the elongation at yield was 13%, theelongation at break was 85%, and the Izod impact strength was as high as641 J/m². These results are shown in Table 2.

COMPARATIVE EXAMPLE 5

With respect to a commercially available polylactic acid “RACEA H-440”(produced by Mitsui Chemicals, Inc.), the 5% thermal reductiontemperature in a nitrogen atmosphere was measured and found to be 320°C. This result is shown in Table 4.

EXAMPLE 13

Into a reaction vessel, 15.8 parts by weight (0.211 mol) oftricyclodecanedimethanol (hereinafter simply referred to as “TCDDM”),57.4 parts by weight (0.709 mol) of DPC and 2.14×10⁻⁴ parts by weight(1.73×10⁻⁶ mol) of cesium carbonate as a catalyst were charged per 26.9parts by weight (0.483 mol) of isosorbide. As a first step of thereaction, these raw materials were dissolved under heating at a heatingbath temperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 15 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 40 minutes and while elevating the heating bath temperature to 190°C. over 40 minutes, the generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the heating bath temperature was elevated to 220° C. over30 minutes. Furthermore, 10 minutes after the start of temperature rise,the pressure in the reaction vessel was adjusted to 0.200 kPa or lessover 30 minutes, and the generated phenol was distilled out. Afterreaching a predetermined stirring torque, the reaction was completed,and the reaction product produced was extruded into water to obtainpellets of a polycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.640dl/g, the glass transition temperature Tig was 126° C., and the color bvalue was 4.6. These results are shown in Table 1.

This polycarbonate copolymer was molded at 245° C. and a moldtemperature of 90° C. to obtain a test specimen having a length of 31.5mm, a width of 6.2 mm and a thickness of 3.2 mm and a tensile testspecimen having a parallel part length of 9 mm and a parallel partdiameter of 1.5 mm. Using these test specimens, evaluation of mechanicalproperties was performed, as a result, the tensile yield strength was 89MPa, the tensile yield modulus was 834 MPa, the elongation at yield was15%, the elongation at break was 76%, and the Izod impact strength was48 J/m². These results are shown in Table 2.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.5095 and the Abbe number was 62. These resultsare shown in Table 3.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 348° C. This results is shown in Table 4.

Furthermore, the photoelastic coefficient was measured and found to be9×10⁻¹² Pa⁻¹. This result is shown in Table 5 together with the value ofthe glass transition temperature.

Also, the amount of the generated gas was examined, as a result, theamount of the generated gas other than the phenol component was 4.5ng/cm², and the generated gas derived from dihydroxy compounds excludingthe dihydroxy compound represented by formula (1) was not detected.These results are shown in Table 6.

In addition, the pencil hardness was F. This result is shown in Table 7.

EXAMPLE 14

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 5.4 parts by weight (0.075 mol) ofTCDDM, 59.0 parts by weight (0.748 mol) of DPC and 2.20×10⁻⁴ parts byweight (1.83×10⁻⁶ mol) of cesium carbonate as a catalyst per 35.5 partsby weight (0.660 mol) of isosorbide.

The reduced viscosity of the obtained polycarbonate copolymer was 0.546dl/g, the glass transition temperature Tig was 144° C., and the color bvalue was 6.4. These results are shown in Table 1.

Evaluation of mechanical properties was performed, as a result, thetensile yield strength was 106 MPa, the tensile yield modulus was 872MPa, the elongation at yield was 16%, the elongation at break was 26%,and the Izod impact strength was 65 J/m². These results are shown inTable 2.

Also, when formed into a film, the refractive index for d line was1.5052, and the Abbe number was 60. These results are shown in Table 3.

EXAMPLE 15

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 10.7 parts by weight (0.145 mol) ofTCDDM, 58.2 parts by weight (0.725 mol) of DPC and 2.17×10⁻⁴ parts byweight (1.78×10⁻⁶ mol) of cesium carbonate as a catalyst per 31.1 partsby weight (0.569 mol) of isosorbide.

The reduced viscosity of the obtained polycarbonate copolymer was 0.644dl/g, the glass transition temperature Tig was 136° C., and the color bvalue was 2.8. These results are shown in Table 1.

Evaluation of mechanical properties was performed, as a result, thetensile yield strength was 107 MPa, the tensile yield modulus was 934MPa, the elongation at yield was 16%, the elongation at break was 39%,and the Izod impact strength was 58 J/m². These results are shown inTable 2.

Also, when formed into a film, the refractive index for d line was1.5090, and the Abbe number was 61. These results are shown in Table 3.

Furthermore, the 5% thermal reduction temperature of the polycarbonatecopolymer in a nitrogen atmosphere was 344° C. This result is shown inTable 4.

EXAMPLE 16

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 20.7 parts by weight (0.274 mol) ofTCDDM, 56.6 parts by weight (0.684 mol) of DPC and 2.11×10⁻⁴ parts byweight (1.68×10⁻⁶ mol) of cesium carbonate as a catalyst per 22.7 partsby weight (0.403 mol) of isosorbide.

The reduced viscosity of the obtained polycarbonate copolymer was 0.637dl/g, the glass transition temperature Tig was 118° C., and the color bvalue was 2.3. These results are shown in Table 1.

Also, when formed into a film, the refractive index for d line was1.5135, and the Abbe number was 58. These results are shown in Table 3.

Furthermore, the photoelastic coefficient was measured and found to be7×10⁻¹² Pa⁻¹. This result is shown in Table 5 together with the value ofthe glass transition temperature.

EXAMPLE 17

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 25.6 parts by weight (0.333 mol) ofTCDDM, 55.8 parts by weight (0.666 mol) of DPC and 2.08×10⁻⁴ parts byweight (1.63×10⁻⁶ mol) of cesium carbonate as a catalyst per 18.7 partsby weight (0.327 mol) of isosorbide.

The reduced viscosity of the obtained polycarbonate copolymer was 0.785dl/g, the glass transition temperature Tig was 110° C., and the color bvalue was 4.7. These results are shown in Table 1.

Evaluation of mechanical properties was performed, as a result, thetensile yield strength was 79 MPa, the tensile yield modulus was 807MPa, the elongation at yield was 13%, the elongation at break was 18%,and the Izod impact strength was 58 J/m². These results are shown inTable 2.

Also, when formed into a film, the refractive index for d line was1.5157, and the Abbe number was 60. These results are shown in Table 3.

Furthermore, the 5% thermal reduction temperature of the polycarbonatecopolymer in a nitrogen atmosphere was 349° C. This result is shown inTable 4.

EXAMPLE 18

As a first step of the reaction, 30.3 parts by weight (0.394 mol) ofTCDDM, 55.0 parts by weight (0.656 mol) of DPC and 2.05×10⁻⁴ parts byweight (1.61×10⁻⁶ mol) of cesium carbonate as a catalyst per 14.7 partsby weight (0.257 mol) of isosorbide were heated at a heating bathtemperature of 150° C. while stirring, if desired, in a nitrogenatmosphere, thereby dissolving the raw materials (about 15 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 3 minutes and while elevating the heating bath temperature to 190°C. over 60 minutes, the generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 6.67kPa, the heating bath temperature was elevated to 240° C. over 45minutes, and the generated phenol was extracted outside of the reactionvessel. Furthermore, the pressure in the reaction vessel was allowed toreach 0.200 kPa or less so as to remove the generated phenol. Afterreaching a predetermined stirring torque, the reaction was completed,and the reaction product produced was extruded into water to obtainpellets of a polycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.672dl/g, the glass transition temperature Tig was 102° C., and the color bvalue was 9.2. These results are shown in Table 1.

Evaluation of mechanical properties was performed, as a result, thetensile yield strength was 76 MPa, the tensile yield modulus was 850MPa, the elongation at yield was 12%, the elongation at break was 31%,and the Izod impact strength was 40 J/m². These results are shown inTable 2.

Also, when formed into a film, the refractive index for d line was1.5185 and the Abbe number was 58. These results are shown in Table 3.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 352° C. This results is shown in Table 4.

COMPARATIVE EXAMPLE 6

Into a reaction vessel, 47.8 parts by weight (0.586 mol) of TCDDM, 58.2parts by weight (0.585 mol) of DPC and 1.95×10⁻⁴ parts by weight(1.44×10⁻⁶ mol) of cesium carbonate as a catalyst were charged. As afirst step of the reaction, these raw materials were dissolved underheating at a heating bath temperature of 150° C. while stirring, ifdesired, in a nitrogen atmosphere (about 15 minutes).

Subsequently, while reducing the pressure from normal pressure to 13.3kPa over 40 minutes, the heating bath temperature was elevated to 190°C. over 40 minutes. The generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the heating bath temperature was elevated to 220° C. over30 minutes. Furthermore, 10 minutes after the start of temperature rise,the pressure in the reaction vessel was adjusted to 0.200 kPa or lessover 30 minutes, and the generated phenol was distilled out. Afterreaching a predetermined stirring torque, the reaction was completed,and the reaction product produced was extruded into water to obtainpellets of a polycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.899dl/g, the glass transition temperature was 73° C., and the color b valuewas 3.9. These results are shown in Table 1.

EXAMPLE 19

Into a reaction vessel, 19.7 parts by weight (0.145 mol) ofpentacyclopentadecanedimethanol (hereinafter simply referred to as“PCPDM”), 54.7 parts by weight (0.494 mol) of DPC and 2.04×10⁻⁴ parts byweight (1.21×10⁻⁶ mol) of cesium carbonate as a catalyst were chargedper 25.6 parts by weight (0.339 mol) of isosorbide. As a first step ofthe reaction, these raw materials were dissolved under heating at aheating bath temperature of 150° C. while stirring, if desired, in anitrogen atmosphere (about 15 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 40 minutes and while elevating the heating bath temperature to 220°C. over 70 minutes, the generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 220° C. for 10 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 0.200kPa or less over 30 minutes while elevating the heating bath temperatureto 240° C. over 20 minutes, and the generated phenol was distilled off.After reaching a predetermined stirring torque, the reaction wascompleted, and the reaction product produced was extruded into water toobtain pellets of a polycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.730dl/g, the glass transition temperature Tig was 149° C., and the color bvalue was 8.4. These results are shown in Table 1.

Also, when this polycarbonate copolymer was pressed at 200° C. andformed into a film having a thickness of about 200 μm, the refractiveindex for d line was 1.5194 and the Abbe number was 60. These resultsare shown in Table 3.

The 5% thermal reduction temperature of the polycarbonate copolymer in anitrogen atmosphere was 347° C. This results is shown in Table 4.

Furthermore, the photoelastic coefficient was measured and found to be8×10⁻¹² Pa⁻¹. This result is shown in Table 5 together with the value ofthe glass transition temperature.

EXAMPLE 20

Into a reaction vessel, 31.5 parts by weight (0.161 mol) ofadamantanedimethanol, 116.8 parts by weight (0.545 mol) of DPC and6.12×10⁻⁴ parts by weight (4.84×10⁻⁶ mol) of cesium carbonate as acatalyst were charged per 54.7 parts by weight (0.374 mol) ofisosorbide. As a first step of the reaction, these raw materials weredissolved under heating at a heating bath temperature of 150° C. whilestirring, if desired, in a nitrogen atmosphere (about 15 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 40 minutes and while elevating the heating bath temperature to 220°C. over 70 minutes, the generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 220° C. for 10 minutes, as asecond step, the pressure in the reaction vessel was adjusted to 0.200kPa or less over 30 minutes while elevating the heating bath temperatureto 230° C. over 20 minutes, and the generated phenol was distilled off.After reaching a predetermined stirring torque, the reaction wascompleted, and the reaction product produced was extruded into water toobtain pellets of a polycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.409dl/g, the glass transition temperature Tig was 125° C., and the color bvalue was 14.8. These results are shown in Table 1.

EXAMPLE 21

The reaction was performed in the same manner as in Example 20 exceptfor changing the raw materials to 31.7 parts by weight (0.160 mol) ofbicyclohexanediol, 116.4 parts by weight (0.543 mol) of DPC and2.04×10⁻⁴ parts by weight (1.21×10⁻⁶ mol) of cesium carbonate as acatalyst per 54.5 parts by weight (0.373 mol) of isosorbide.

The reduced viscosity of the obtained polycarbonate copolymer was 0.260dl/g, the glass transition temperature Tig was 125° C., and the color bvalue was 8.6. These results are shown in Table 1.

EXAMPLE 22

Into a reaction vessel, 30.0 parts by weight (0.428 mol) of 1,4-CHDM,58.3 parts by weight (0.561 mol) of DPC and 2.18×10⁻⁴ parts by weight(1.38×10⁻⁶ mol) of cesium carbonate as a catalyst were charged per 11.7parts by weight (0.165 mol) of isosorbide. As a first step of thereaction, these raw materials were dissolved under heating at a heatingbath temperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 15 minutes).

Subsequently, the pressure was adjusted from normal pressure to 13.3 kPaand while elevating the heating bath temperature to 190° C. over 1 hour,the generated phenol was extracted outside of the system. After keepingat 190° C. for 30 minutes, as a second step, the pressure in thereaction vessel was adjusted to 6.67 kPa, the heating bath temperaturewas elevated to 220° C. over 45 minutes, and the generated phenol wasextracted. With an increase in the stirring torque, the pressure in thereaction vessel was allowed to reach 0.200 kPa or less so as to furtherremove the generated phenol. After reaching a predetermined stirringtorque, the reaction was completed, and the reaction product wasextruded into water to obtain pellets.

The reduced viscosity of the obtained polycarbonate copolymer was 0.979dl/g, the glass transition temperature was 74° C., and the color b valuewas 4.7. These results are shown in Table 1.

Furthermore, this polycarbonate copolymer was pressed at 200° C. toobtain a film having a thickness of about 200 μm. The refractive indexfor d line was 1.5002, and the Abbe number was 56. These results areshown in Table 3.

EXAMPLE 23

The reaction was performed in the same manner as in Example 22 exceptfor changing the raw materials to 7.8 parts by weight (0.142 mol) ofisosorbide, 34.1 parts by weight (0.631 mol) of 1,4-CHDM, 58.1 parts byweight (0.723 mol) of DPC and 2.17×10⁻⁴ parts by weight (1.77×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 1.159dl/g, the glass transition temperature Tig was 63° C., and the color bvalue was 2.9. These results are shown in Table 1.

Furthermore, this polycarbonate copolymer was pressed at 200° C. toobtain a film having a thickness of about 200 μm. The refractive indexfor d line was 1.5024, and the Abbe number was 56. These results areshown in Table 3.

EXAMPLE 24

The reaction was performed in the same manner as in Example 22 exceptfor changing the raw materials to 3.9 parts by weight (0.070 mol) ofisosorbide, 38.2 parts by weight (0.703 mol) of 1,4-CHDM, 57.9 parts byweight (0.717 mol) of DPC and 2.16×10⁻⁴ parts by weight (1.76×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.670dl/g, the glass transition temperature Tig was 51° C., and the color bvalue was 2.8. These results are shown in Table 1.

EXAMPLE 25

The reaction was performed in the same manner as in Example 22 exceptfor changing the raw materials to 1.9 parts by weight (0.035 mol) ofisosorbide, 40.3 parts by weight (0.740 mol) of 1,4-CHDM, 57.8 parts byweight (0.715 mol) of DPC and 2.15×10⁻⁴ parts by weight (1.75×10⁻⁶ mol)of cesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.640dl/g, the glass transition temperature Tig was 45° C., and the color bvalue was 3.0. These results are shown in Table 1.

COMPARATIVE EXAMPLE 7

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 85.61 parts by weight (0.585 mol) ofisosorbide, 22.6 parts by weight (0.251 mol) of 1,4-butanediol(hereinafter simply referred to as “1,4-BG”), 166.8 parts by weight(0.779 mol) of DPC and 1.08×10⁻⁴ parts by weight (0.87×10⁻⁶ mol) ofcesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.568dl/g, the glass transition temperature was 116° C., and the color bvalue was 12.4. These results are shown in Table 1.

Also, the photoelastic coefficient was measured and found to be 23×10⁻¹²Pa⁻¹. This result is shown in Table 5 together with the value of theglass transition temperature.

Furthermore, the amount of the generated gas was examined, as a result,the amount of the generated gas other than the phenol component was 10.0ng/cm², and 2.0 ng/cm² of tetrahydrofuran (THF) was detected as thegenerated gas derived from dihydroxy compounds excluding the dihydroxycompound represented by formula (1). These results are shown in Table 6.

COMPARATIVE EXAMPLE 8

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 81.22 parts by weight (0.556 mol) ofisosorbide, 28.2 parts by weight (0.239 mol) of 1,6-hexanediol(hereinafter simply referred to as “1,6-HD”), 161.6 parts by weight(0.754 mol) of DPC and 1.08×10⁻⁴ parts by weight (0.87×10⁻⁶ mol) ofcesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 1.063dl/g, the glass transition temperature was 85° C., and the color b valuewas 8.9. These results are shown in Table 1.

Also, the photoelastic coefficient was measured and found to be 20×10⁻¹²Pa⁻¹. This result is shown in Table 5 together with the value of theglass transition temperature.

Furthermore, the amount of the generated gas was examined, as a result,the amount of the generated gas other than the phenol component was 11.0ng/cm², and 5.6 ng/cm² of cyclohexadiene and cyclohexyl phenyl ether wasdetected as the generated gas derived from dihydroxy compounds excludingthe dihydroxy compound represented by formula (1). These results areshown in Table 6.

In addition, the pencil hardness was HB. This result is shown in Table7.

COMPARATIVE EXAMPLE 9

The reaction was performed in the same manner as in Example 7 except forchanging the raw materials to 42.6 parts by weight (0.292 mol) ofisosorbide, 25.6 parts by weight (0.130 mol) of TCDDM, 46.7 parts byweight (0.106 mol) of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene(hereinafter simply referred to as “BHEPF”), 127.6 parts by weight(0.596 mol) of DPC and 8.7×10⁻⁵ parts by weight (5.9×10⁻⁶ mol) of sodiumhydroxide as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.659dl/g, the glass transition temperature was 121° C., and the color bvalue was 9.2. These results are shown in Table 1.

Furthermore, this polycarbonate copolymer was pressed at 200° C. toobtain a film having a thickness of 200 μm. The refractive index for dline was 1.5410, and the Abbe number was 42. These results are shown inTable 3.

COMPARATIVE EXAMPLE 10

The reaction was performed in the same manner as in Example 13 exceptfor changing the raw materials to 63.84 parts by weight (0.437 mol) ofisosorbide, 27.6 parts by weight (0.0729 mol) of 9,9-biscresolfluorene(hereinafter simply referred to as “BCF”), 19.7 parts by weight (0.219mol) of 1,4-butanediol and 1.08×10⁻⁴ parts by weight (0.87×10⁻⁶ mol) ofcesium carbonate as a catalyst.

The reduced viscosity of the obtained polycarbonate copolymer was 0.464dl/g, the glass transition temperature was 129° C., and the color bvalue was 8.3. These results are shown in Table 1.

Also, the photoelastic coefficient was measured and found to be 23×10⁻¹²Pa⁻¹. This result is shown in Table 5 together with the value of theglass transition temperature.

EXAMPLE 26

Into a reaction vessel, 15.4 parts by weight (8.02 mol) of TCDDM, 57.7parts by weight (26.72 mol) of DPC and 2.14×10⁻⁴ parts by weight(6.68×10⁻⁵ mol) of cesium carbonate as a catalyst were charged per 26.8parts by weight (18.70 mol) of isosorbide. As a first step of thereaction, these raw materials were dissolved under heating at a heatingbath temperature of 150° C. while stirring, if desired, in a nitrogenatmosphere (about 60 minutes).

Subsequently, the pressure was reduced from normal pressure to 13.3 kPaover 40 minutes and while elevating the heating bath temperature to 190°C. over 40 minutes, the generated phenol was extracted outside of thereaction vessel.

After keeping the entire reaction vessel at 190° C. for 15 minutes, as asecond step, the heating bath temperature was elevated to 220° C. over30 minutes, and 10 minutes after the temperature reached 220° C., thepressure in the reaction vessel adjusted to 0.200 kPa or less over 30minutes to distill out the generated phenol. After reaching apredetermined stirring torque, the reaction was completed, and thereaction product produced was extruded into water to obtain pellets of apolycarbonate copolymer.

The reduced viscosity of the obtained polycarbonate copolymer was 0.506dl/g, the glass transition temperature Tig was 126° C., and the color bvalue was 10.0. These results are shown in Table 8.

Also, FIG. 2 shows the NMR chart of this polycarbonate copolymer.

EXAMPLE 27

The reaction was performed in the same manner as in Example 26 exceptfor changing the raw materials to 12.7 parts by weight (9.47 mol) ofCHDM, 60.4 parts by weight (30.39 mol) of DPC and 2.15×10⁻⁴ parts byweight (7.10×10⁻⁵ mol) of cesium carbonate as a catalyst per 26.9 partsby weight (19.88 mol) of isosorbide. The reduced viscosity of theobtained polycarbonate copolymer was 0.621 dl/g, the glass transitiontemperature Tig was 123° C., and the color b value was 11.0. Theseresults are shown in Table 8.

Distillation of Isosorbide:

Isosorbide (about 1.3 kg) was charged into a 2 L-volume flask in anargon stream, a Claisen tube was attached to the flask, and a receivingvessel was fixed through a fraction cutter. The parts such as pipelineeach was kept warm to avoid solidification. After the initiation ofgradual reduction of the pressure, when the system was heated, thecompound was dissolved at an inner temperature of about 100° C. andthereafter, started distilling out at an inner temperature of 160° C. Atthis time, the pressure was at 133 to 266 Pa. The initial distillate wasremoved and then, distillation was performed at an inner temperature of160 to 170° C., a top temperature of 150 to 157° C. and 133 Pa. Afterthe completion of distillation, the pressure was returned to normalpressure by introducing argon. The obtained distillation product wascooled and ground under an argon stream to obtain isosorbide. Thisproduct was sealed in an aluminum-laminated bag under an argon streamand stored.

EXAMPLES 28 AND 29

The reaction was performed in the same manner as in Example 13 exceptfor using ISOB in which the formic acid content was adjusted to theamount shown in Table 8 by previously distilling ISOB.

The obtained polycarbonate copolymers each was measured for the reducedviscosity, glass transition temperature and color b value, and theresults are shown in Table 8.

EXAMPLES 30 AND 31

The reaction was performed in the same manner as in Example 2 except forusing ISOB in which the formic acid content was adjusted to the amountshown in Table 8 by previously distilling ISOB.

The obtained polycarbonate copolymers each was measured for the reducedviscosity, glass transition temperature and color b value, and theresults are shown in Table 8.

REFERENCE EXAMPLES 1 TO 3

The reaction was performed in the same manner as in Example 13 exceptfor using ISOB in which the formic acid content was the amount shown inTable 8 without previously distilling ISOB.

Phenol was distilled out, but the reaction solution was graduallycolored, an increase in the torque was not observed, and a polymer wasnot obtained.

REFERENCE EXAMPLE 4

The reaction was performed in the same manner as in Example 2 except forusing ISOB in which the formic acid content was the amount shown inTable 8 without previously distilling ISOB.

Phenol was distilled out, but the reaction solution was graduallycolored, an increase in the torque was not observed, and a polymer wasnot obtained.

TABLE 1 Charge Parts by Weight Dihydroxy Compounds Other Than ChargeMolar Ratio ISOB Dihydroxy Ratio of DPC to ISOB (parts parts by DPC(parts Compounds Other All Dihydroxy by weight) kind weight by weight)ISOB than ISOB Compounds Example 1 27.7 1,4-CHDM 13.0 59.2 0.68 0.320.99 Example 2 31.8 1,4-CHDM 8.7 59.5 0.78 0.22 1.00 Example 3 35.91,4-CHDM 4.4 59.7 0.89 0.11 1.01 Example 4 19.7 1,4-CHDM 21.6 58.8 0.470.53 0.97 Example 5 15.7 1,4-CHDM 25.8 58.6 0.37 0.63 0.96 Example 627.7 1,4-CHDM 13.0 59.2 0.68 0.32 0.99 Example 7 27.7 1,4-CHDM 13.0 59.20.68 0.32 0.99 Example 8 28.2 1,4-CHDM 13.3 58.5 0.68 0.32 0.96 Example9 27.7 1,4-CHDM 13.0 59.2 0.68 0.32 0.99 Example 10 27.7 1,4-CHDM 13.059.2 0.68 0.32 0.99 Example 11 27.7 1,4-CHDM 13.0 59.2 0.68 0.32 0.99Example 12 19.7 1,4-CHDM 21.6 58.8 0.47 0.53 0.97 Example 13 26.9 TCDDM15.8 57.4 0.7 0.3 1.01 Example 14 35.5 TCDDM 5.4 59.0 0.9 0.1 1.02Example 15 31.1 TCDDM 10.7 58.2 0.8 0.2 1.02 Example 16 22.7 TCDDM 20.756.6 0.6 0.4 1.00 Example 17 18.7 TCDDM 25.6 55.8 0.5 0.5 1.01 Example18 14.7 TCDDM 30.3 55.0 0.4 0.6 1.01 Example 19 25.6 PCPDM 19.7 54.7 0.70.3 1.02 Example 20 54.7 adamantanedimethanol 31.5 116.8 0.7 0.3 1.02Example 21 54.5 biscyclohxanediol 31.7 116.4 0.7 0.3 1.02 Example 2211.7 1,4-CHDM 30.0 58.3 0.28 0.78 0.95 Example 23 7.8 1,4-CHDM 34.1 58.10.18 0.82 0.94 Example 24 3.9 1,4-CHDM 38.2 57.9 0.09 0.91 0.93 Example25 1.9 1,4-CHDM 40.3 57.8 0.05 0.95 0.92 Comparative Example 1 40.1 —0.0 59.9 1.00 0.00 1.02 Comparative Example 2 0.0 1,4-CHDM 42.3 57.70.00 1.00 0.92 Comparative Example 6 0.0 TCDDM 47.8 58.2 0.00 1.00 1.00Comparative Example 7 85.61 1,4-BG 22.6 166.8 0.7 0.3 0.93 ComparativeExample 8 81.22 1,6-HD 28.2 161.6 0.7 0.3 0.95 Comparative Example 942.6 TCDDM/BHEPF 25.6/46.7 127.6 0.5 0.4/0.1 1.02 Comparative Example 1063.84 BCF/1,4-BG 27.6/19.7 145.04 0.6 0.1/0.3 0.93 Glass CatalystPolymerization Reduced Transition amount added Stabilizer TemperatureViscosity Temperature kind Note 1) Note 2) (° C.) (dl/g) Tig (° C.)Color b Example 1 cesium carbonate 5 — 250 1.007 124 8.8 Example 2cesium carbonate 5 — 240 0.757 133 8.2 Example 3 cesium carbonate 5 —240 0.712 148 9.1 Example 4 cesium carbonate 5 — 250 1.196 101 7.7Example 5 cesium carbonate 5 — 240 1.186 89 5.1 Example 6 cesiumcarbonate 5 — 240 0.979 124 9.5 Example 7 sodium hydroxide 8 — 240 0.965123 9.4 Example 8 cesium carbonate 5 — 250 0.496 122 9.6 Example 9cesium carbonate 0.5 — 240 0.910 124 9.8 Example 10 cesium carbonate 25— 240 0.980 124 8.3 Example 11 cesium carbonate 5 PEP-36 240 0.975 1247.2 Example 12 cesium carbonate 5 PEP-36 240 0.850 100 3.6 Example 13cesium carbonate 5 220 0.640 126 4.6 Example 14 cesium carbonate 5 2200.546 144 6.4 Example 15 cesium carbonate 5 220 0.644 136 2.8 Example 16cesium carbonate 5 220 0.637 118 2.3 Example 17 cesium carbonate 5 2200.785 110 4.7 Example 18 cesium carbonate 5 240 0.672 102 9.2 Example 19cesium carbonate 5 240 0.730 149 8.4 Example 20 cesium carbonate 15 2300.409 125 14.8 Example 21 cesium carbonate 5 230 0.260 125 8.6 Example22 cesium carbonate 5 — 220 0.979 74 4.7 Example 23 cesium carbonate 5 —220 1.159 63 2.9 Example 24 cesium carbonate 5 — 220 0.670 51 2.8Example 25 cesium carbonate 5 — 220 0.640 45 3.0 Comparative Example 1cesium carbonate 5 — 250 0.679 160 13.0 Comparative Example 2 cesiumcarbonate 5 — 220 0.662 40 4.5 Comparative Example 6 cesium carbonate 5220 0.899 73 3.9 Comparative Example 7 Mg acetate 2.5 220 0.568 116 12.4Comparative Example 8 cesium carbonate 2.5 220 1.063 85 8.9 ComparativeExample 9 sodium hydroxide 8 240 0.659 121 9.2 Comparative Example 10cesium carbonate 2.5 220 0.464 129 8.3 Note 1) Molar number (unit: μmol)as metal per mol of all dihydroxy compounds. Note 2) Amount of PEP-36added: 0.096 parts by weight in Examples 15 and 16.

TABLE 2 Tensile Tensile Izod Charge Molar Ratio of Reduced Yield YieldElongation Elongation Impact Dihydroxy Compounds Viscosity StrengthModulus at Yield at Break Strength Isosorbide 1,4-CHDM TCDDM (dl/g)(MPa) (MPa) (%) (%) (J/m²) Example 1 0.68 0.32 1.007 84 748 16 30 227Example 4 0.47 0.53 1.196 66 595 16 27 293 Example 5 0.37 0.63 1.186 59541 15 70 784 Example 6 0.68 0.32 0.979 78 691 16 47 184 Example 13 0.70.3 0.640 89 834 15 76 48 Example 14 0.9 0.1 0.546 106 872 16 26 65Example 15 0.8 0.2 0.644 107 934 16 39 58 Example 17 0.5 0.5 0.785 79807 13 18 58 Example 18 0.4 0.6 0.672 76 850 12 31 40 Comparative 1.00.0 0.679 105 353 17 31 11 Example 1 Comparative — — 0.456 63 629 13 746 Example 3 (Iupilon H4000) Comparative — — 0.507 63 565 13 85 641Example 4 (Iupilon S2000)

TABLE 3 Charge Molar Ratio of Dihydroxy Refractive Index Compounds nD nCne nF Abbe Number ISOB 1,4-CHDM TCDDM PCPDM (589 nm) (656 nm) (546 nm)(486 nm) νd Example 1 0.68 0.32 1.4992 1.4969 1.5015 1.5056 58 Example 20.78 0.22 1.5004 1.4980 1.5026 1.5068 57 Example 3 0.89 0.11 1.50141.4991 1.5037 1.5079 57 Example 4 0.47 0.53 1.4993 1.4970 1.5013 1.505261 Example 5 0.37 0.63 1.4993 1.4969 1.5014 1.5050 62 Example 13 0.7 0.31.5095 1.5070 1.5118 1.5153 62 Example 14 0.9 0.1 1.5052 1.5027 1.50731.5111 60 Example 15 0.8 0.2 1.5090 1.5065 1.5113 1.5148 61 Example 160.6 0.4 1.5135 1.5110 1.5158 1.5198 58 Example 17 0.5 0.5 1.5157 1.51311.5180 1.5217 60 Example 18 0.4 0.6 1.5185 1.5159 1.5209 1.5249 58Example 19 0.7 0.3 1.5194 1.5167 1.5215 1.5254 60 Example 22 0.28 0.781.5002 1.4980 1.5026 1.5066 56 Example 23 0.18 0.82 1.5024 1.5000 1.50521.5094 56 Comparative Example 3 1.5828 1.5776 1.5879 1.5970 30 (IupilonH4000) Comparative Example 9 1.5410 1.5374 1.5443 1.5502 42(ISB/TCDDM/BHEPF = 5/4/1)

TABLE 4 Charge Molar Ratio of Dihydroxy Compounds 5% Weight ReductionIsosorbide 1,4-CHDM TCDDM PCPDM 1,4-BG 1,6-HD Temperature (° C.) Example1 0.68 0.32 344 Example 2 0.78 0.22 343 Example 4 0.47 0.53 345 Example13 0.7 0.3 348 Example 15 0.8 0.2 344 Example 17 0.5 0.5 349 Example 180.4 0.6 352 Example 19 0.7 0.3 347 Comparative Example 1 1.0 0.0 339Comparative Example 5 320 (polylactic acid) Comparative Example 7 0.70.3 339 (ISB/1,4-BG = 7/3) Comparative Example 8 0.3 336 (ISB/1,6-HD =7/3)

TABLE 5 Glass Photoelastic Transition Dihydroxy Compound Coefficient,Temper- Charge Com- Charge (×10⁻¹² ature position Molar Ratio Pa⁻¹ ) Tig(° C.) Example 2 ISB/1,4-CHDM 0.78/0.22 20 133 Example 13 ISB/TCDDM0.7/0.3 9 126 Example 16 ISB/TCDDM 0.6/0.4 7 118 Example 19 ISB/PCPDM0.7/0.3 8 149 Comparative Iupilon H4000 72 145 Example 3 ComparativeISB/1,4-BG 0.7/0.3 23 116 Example 7 Comparative ISB/1,6-HD 0.7/0.3 20 85 Example 8 Comparative ISOB/BG/BCF 0.6/0.3/0.1 23 129 Example 10

TABLE 6 Amount of Generated Gas Derived From Dihydroxy CompoundsGeneration Excluding of Gas Dihydroxy Dihydroxy Compound Other ThanCompound Charge Phenol Represented by Charge Molar Component Formula (1)Composition Ratio (ng/cm²) (ng/cm²) Example 1 ISOB/CHDM 0.68/0.32 3.70   Example 13 ISOB/TCDDM 0.7/0.3 4.5 0   Comparative ISOB/1,4-BG0.7/0.3 10.0 2.0¹⁾ Example 7 Comparative ISOB/1,6-HD 0.7/0.3 11.0 5.6²⁾Example 8 ¹⁾THF ²⁾Cyclohexadiene, cyclohexyl phenyl ether

TABLE 7 Charge Molar Ratio of Pencil Dihydroxy Compounds HardnessExample 6 ISB/CHDM = 0.68/0.32 H Example 8 ISB/CHDM = 0.68/0.32 HExample 13 ISB/TCDDM = 0.7/0.3 F Comparative Example 3 (Iupilon H4000)2B Comparative Example 8 ISB/1,6-HD = 0.7/0.3 HB

TABLE 8 Presence Amount of Glass or Absence Formic Transition of Distil-Acid in Reduced Temperature lation of ISOB Viscosity Tig Color ISOB(PPM) (dl/g) (° C.) b Example 26 none 5 0.506 126 10.0 Example 27 none 50.621 123 11.0 Example 28 distilled 3 0.510 126 4.5 Example 29 distilled2 0.640 126 3.7 Example 30 distilled 3 0.658 123 7.0 Example 31distilled 2 0.590 123 6.5 Reference none 400 not — — Example 1polymerized Reference none 50 not — — Example 2 polymerized Referencenone 20 not — — Example 3 polymerized Reference none 50 not — — Example4 polymerized

As seen from Table 2, the polycarbonate copolymer of the presentinvention exhibits tensile yield strength, tensile yield modulus andelongation at yield equal to or greater than those of the commerciallyavailable polycarbonates and has high Izod impact strength.

As seen from Table 3, the polycarbonate copolymer of the presentinvention has a small refractive index and a large Abbe number ascompared with the commercially available polycarbonate or conventionalpolycarbonate.

As seen from Table 4, the polycarbonate copolymer of the presentinvention has high thermal stability as compared with the commerciallyavailable polylactic acid or conventional polycarbonate.

It is understood from these results that the polycarbonate copolymer ofthe present invention has excellent mechanical strength, good thermalstability, small refractive index, large Abbe number and hightransparency and can be suitably used for an optical material or variousmolding materials.

As seen from Table 5, the polycarbonate copolymer of the presentinvention has a small photoelastic coefficient and can be suitably usedfor a film or an optical material such as lens.

As seen from Table 6, the polycarbonate of the present inventionobtained by copolymerizing an alicyclic dihydroxy compound is smaller inthe amount of the generated gas than the polycarbonate obtained bycopolymerizing an aliphatic diol. That is, when an aliphatic diol suchas 1,4-butanediol and 1,6-hexanediol is used as a dihydroxy compound,generation of a gas derived from the diol, such as cyclic ether, isobserved, but when an alicyclic diol such as cyclohexanedimethanol andtricyclodecanedimethanol is used, this generated gas is scarcelyobserved. Accordingly, it is revealed that the alicyclic diol-containingpolycarbonate less affects the environment when used in home electricappliances and the like, such as optical film.

As seen from Table 7, the polycarbonate copolymer of the presentinvention has high pencil hardness and can be suitably used for filmusage or structure material usage such as housing, in which high surfacehardness is required and the surface is averse to scratching.

As seen from Table 8, a polycarbonate copolymer more reduced incoloration can be obtained by using isosorbide from which formic acid isremoved by distillation or the like.

While the present invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof.

This application is based on Japanese Patent Application (PatentApplication No. 2006-168929) filed on Jun. 19, 2006, the contents ofwhich are incorporated herein by way of reference.

INDUSTRIAL APPLICABILITY

The polycarbonate copolymer of the present invention is suitably used inthe field of film or sheet requiring flexibility, in the field of bottleor container requiring heat resistance, for various structure materialsrequiring impact strength, for lens usage such as camera lens,viewfinder lens and lens for CCD or CMOS, for usage as a film or sheetsuch as phase difference film, diffusing sheet or polarizing filmutilized in a liquid crystal display, a plasma display device or thelike, and for usage as an optical disc, film or sheet, as an opticalmaterial, as an optical component or as a binder for fixing a dye, acharge transfer agent or the like.

1. A method of producing a polycarbonate copolymer, comprising reactinga dihydroxy compound represented by the following formula (1) and analicyclic dihydroxy compound with a carbonic acid diester in thepresence of a polymerization catalyst:

wherein the polycarbonate copolymer comprises a constitutional unitderived from the dihydroxy compound represented by the formula (1) and aconstitutional unit derived from an alicyclic dihydroxy compound,wherein the Abbe number is 50 or more and the 5% thermal reductiontemperature is 340° C. or more.
 2. A method of producing a polycarbonatecopolymer, comprising reacting a dihydroxy compound represented by thefollowing formula (1) and an alicyclic dihydroxy compound with acarbonic acid diester in the presence of a polymerization catalyst:

wherein the polycarbonate copolymer comprises a constitutional unitderived from the dihydroxy compound represented by the formula (1) and aconstitutional unit derived from an alicyclic dihydroxy compound,wherein the ratio of the dihydroxy compound represented by the formula(1) and the alicyclic dihydroxy compound to all dihydroxy compoundsconstituting said copolymer is 90 mol % or more.
 3. The method ofproducing the polycarbonate copolymer according to claim 1, wherein analkali metal compound, an alkaline earth metal compound or both thecompounds are used as the polymerization catalyst.
 4. The method ofproducing the of producing the polycarbonate copolymer according toclaim 2, wherein an alkali metal compound, an alkaline earth metalcompound or both the compounds are used as the polymerization catalyst.